CN112409935A - Adhesive sheet roll - Google Patents
Adhesive sheet roll Download PDFInfo
- Publication number
- CN112409935A CN112409935A CN202010761033.3A CN202010761033A CN112409935A CN 112409935 A CN112409935 A CN 112409935A CN 202010761033 A CN202010761033 A CN 202010761033A CN 112409935 A CN112409935 A CN 112409935A
- Authority
- CN
- China
- Prior art keywords
- adhesive
- film
- adhesive sheet
- adhesive layer
- meth
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
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- 239000000853 adhesive Substances 0.000 title claims abstract description 393
- 230000001070 adhesive effect Effects 0.000 title claims abstract description 353
- 239000012790 adhesive layer Substances 0.000 claims abstract description 186
- 239000011162 core material Substances 0.000 claims abstract description 37
- 206010040844 Skin exfoliation Diseases 0.000 claims description 48
- 238000003860 storage Methods 0.000 claims description 43
- 239000004820 Pressure-sensitive adhesive Substances 0.000 claims description 16
- 239000005361 soda-lime glass Substances 0.000 claims description 6
- 238000004804 winding Methods 0.000 abstract description 28
- 229920001577 copolymer Polymers 0.000 description 80
- 239000000178 monomer Substances 0.000 description 78
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 74
- 239000000203 mixture Substances 0.000 description 58
- 239000010410 layer Substances 0.000 description 52
- 239000003431 cross linking reagent Substances 0.000 description 40
- -1 polyethylene Polymers 0.000 description 40
- 230000037303 wrinkles Effects 0.000 description 31
- 238000000034 method Methods 0.000 description 30
- 239000011248 coating agent Substances 0.000 description 29
- 238000000576 coating method Methods 0.000 description 29
- 238000012360 testing method Methods 0.000 description 25
- 239000000463 material Substances 0.000 description 24
- 229920000642 polymer Polymers 0.000 description 22
- 125000000217 alkyl group Chemical group 0.000 description 21
- 238000004519 manufacturing process Methods 0.000 description 21
- 239000000047 product Substances 0.000 description 19
- 239000000243 solution Substances 0.000 description 18
- 239000011347 resin Substances 0.000 description 17
- 229920005989 resin Polymers 0.000 description 17
- 239000002904 solvent Substances 0.000 description 17
- 125000002723 alicyclic group Chemical group 0.000 description 16
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 15
- 125000004432 carbon atom Chemical group C* 0.000 description 14
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 14
- 230000000052 comparative effect Effects 0.000 description 12
- 239000011521 glass Substances 0.000 description 12
- 239000003999 initiator Substances 0.000 description 11
- 230000001681 protective effect Effects 0.000 description 11
- 238000004132 cross linking Methods 0.000 description 10
- 238000007639 printing Methods 0.000 description 10
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 9
- 239000006087 Silane Coupling Agent Substances 0.000 description 9
- 239000000654 additive Substances 0.000 description 9
- ZFSLODLOARCGLH-UHFFFAOYSA-N isocyanuric acid Chemical class OC1=NC(O)=NC(O)=N1 ZFSLODLOARCGLH-UHFFFAOYSA-N 0.000 description 9
- 229920000139 polyethylene terephthalate Polymers 0.000 description 9
- 239000005020 polyethylene terephthalate Substances 0.000 description 9
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 8
- 230000005856 abnormality Effects 0.000 description 8
- 239000003522 acrylic cement Substances 0.000 description 8
- 238000005259 measurement Methods 0.000 description 8
- 229910052757 nitrogen Inorganic materials 0.000 description 8
- 125000004433 nitrogen atom Chemical group N* 0.000 description 8
- 238000006116 polymerization reaction Methods 0.000 description 8
- 238000005227 gel permeation chromatography Methods 0.000 description 7
- 239000005056 polyisocyanate Substances 0.000 description 7
- 229920001228 polyisocyanate Polymers 0.000 description 7
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 6
- 239000003795 chemical substances by application Substances 0.000 description 6
- 238000007667 floating Methods 0.000 description 6
- 238000010438 heat treatment Methods 0.000 description 6
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 6
- DVKJHBMWWAPEIU-UHFFFAOYSA-N toluene 2,4-diisocyanate Chemical compound CC1=CC=C(N=C=O)C=C1N=C=O DVKJHBMWWAPEIU-UHFFFAOYSA-N 0.000 description 6
- TXBCBTDQIULDIA-UHFFFAOYSA-N 2-[[3-hydroxy-2,2-bis(hydroxymethyl)propoxy]methyl]-2-(hydroxymethyl)propane-1,3-diol Chemical compound OCC(CO)(CO)COCC(CO)(CO)CO TXBCBTDQIULDIA-UHFFFAOYSA-N 0.000 description 5
- 230000000996 additive effect Effects 0.000 description 5
- 230000000694 effects Effects 0.000 description 5
- 238000010528 free radical solution polymerization reaction Methods 0.000 description 5
- 239000002184 metal Substances 0.000 description 5
- 229910052751 metal Inorganic materials 0.000 description 5
- 229920000728 polyester Polymers 0.000 description 5
- 229920001296 polysiloxane Polymers 0.000 description 5
- 230000009257 reactivity Effects 0.000 description 5
- 150000003377 silicon compounds Chemical class 0.000 description 5
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 4
- ZJCCRDAZUWHFQH-UHFFFAOYSA-N Trimethylolpropane Chemical compound CCC(CO)(CO)CO ZJCCRDAZUWHFQH-UHFFFAOYSA-N 0.000 description 4
- 238000007865 diluting Methods 0.000 description 4
- 238000010790 dilution Methods 0.000 description 4
- 239000012895 dilution Substances 0.000 description 4
- 238000010894 electron beam technology Methods 0.000 description 4
- 238000011156 evaluation Methods 0.000 description 4
- 230000001678 irradiating effect Effects 0.000 description 4
- 239000012948 isocyanate Substances 0.000 description 4
- 150000002513 isocyanates Chemical class 0.000 description 4
- 238000010030 laminating Methods 0.000 description 4
- 238000009281 ultraviolet germicidal irradiation Methods 0.000 description 4
- DTGKSKDOIYIVQL-WEDXCCLWSA-N (+)-borneol Chemical group C1C[C@@]2(C)[C@@H](O)C[C@@H]1C2(C)C DTGKSKDOIYIVQL-WEDXCCLWSA-N 0.000 description 3
- PSGCQDPCAWOCSH-UHFFFAOYSA-N (4,7,7-trimethyl-3-bicyclo[2.2.1]heptanyl) prop-2-enoate Chemical compound C1CC2(C)C(OC(=O)C=C)CC1C2(C)C PSGCQDPCAWOCSH-UHFFFAOYSA-N 0.000 description 3
- XLPJNCYCZORXHG-UHFFFAOYSA-N 1-morpholin-4-ylprop-2-en-1-one Chemical compound C=CC(=O)N1CCOCC1 XLPJNCYCZORXHG-UHFFFAOYSA-N 0.000 description 3
- GOXQRTZXKQZDDN-UHFFFAOYSA-N 2-Ethylhexyl acrylate Chemical compound CCCCC(CC)COC(=O)C=C GOXQRTZXKQZDDN-UHFFFAOYSA-N 0.000 description 3
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 3
- OMIGHNLMNHATMP-UHFFFAOYSA-N 2-hydroxyethyl prop-2-enoate Chemical compound OCCOC(=O)C=C OMIGHNLMNHATMP-UHFFFAOYSA-N 0.000 description 3
- SXIFAEWFOJETOA-UHFFFAOYSA-N 4-hydroxy-butyl Chemical group [CH2]CCCO SXIFAEWFOJETOA-UHFFFAOYSA-N 0.000 description 3
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 3
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- DRKNCXJRCPVHNQ-UHFFFAOYSA-N O1CCN(CC1)C(C=C)=O.C(C=C)(=O)N1CCOCC1 Chemical compound O1CCN(CC1)C(C=C)=O.C(C=C)(=O)N1CCOCC1 DRKNCXJRCPVHNQ-UHFFFAOYSA-N 0.000 description 3
- 239000004743 Polypropylene Substances 0.000 description 3
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 description 3
- 239000007983 Tris buffer Substances 0.000 description 3
- 230000002411 adverse Effects 0.000 description 3
- 125000003277 amino group Chemical group 0.000 description 3
- 125000003118 aryl group Chemical group 0.000 description 3
- DKPFZGUDAPQIHT-UHFFFAOYSA-N butyl acetate Chemical compound CCCCOC(C)=O DKPFZGUDAPQIHT-UHFFFAOYSA-N 0.000 description 3
- 150000001875 compounds Chemical class 0.000 description 3
- 239000000976 ink Substances 0.000 description 3
- 229920001155 polypropylene Polymers 0.000 description 3
- 239000007787 solid Substances 0.000 description 3
- BPSIOYPQMFLKFR-UHFFFAOYSA-N trimethoxy-[3-(oxiran-2-ylmethoxy)propyl]silane Chemical compound CO[Si](OC)(OC)CCCOCC1CO1 BPSIOYPQMFLKFR-UHFFFAOYSA-N 0.000 description 3
- ARXJGSRGQADJSQ-UHFFFAOYSA-N 1-methoxypropan-2-ol Chemical compound COCC(C)O ARXJGSRGQADJSQ-UHFFFAOYSA-N 0.000 description 2
- OZAIFHULBGXAKX-UHFFFAOYSA-N 2-(2-cyanopropan-2-yldiazenyl)-2-methylpropanenitrile Chemical compound N#CC(C)(C)N=NC(C)(C)C#N OZAIFHULBGXAKX-UHFFFAOYSA-N 0.000 description 2
- KANZWHBYRHQMKZ-UHFFFAOYSA-N 2-ethenylpyrazine Chemical compound C=CC1=CN=CC=N1 KANZWHBYRHQMKZ-UHFFFAOYSA-N 0.000 description 2
- ZNQVEEAIQZEUHB-UHFFFAOYSA-N 2-ethoxyethanol Chemical compound CCOCCO ZNQVEEAIQZEUHB-UHFFFAOYSA-N 0.000 description 2
- 125000000954 2-hydroxyethyl group Chemical group [H]C([*])([H])C([H])([H])O[H] 0.000 description 2
- NJWGQARXZDRHCD-UHFFFAOYSA-N 2-methylanthraquinone Chemical compound C1=CC=C2C(=O)C3=CC(C)=CC=C3C(=O)C2=C1 NJWGQARXZDRHCD-UHFFFAOYSA-N 0.000 description 2
- KWOLFJPFCHCOCG-UHFFFAOYSA-N Acetophenone Chemical compound CC(=O)C1=CC=CC=C1 KWOLFJPFCHCOCG-UHFFFAOYSA-N 0.000 description 2
- 239000004593 Epoxy Substances 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- JOYRKODLDBILNP-UHFFFAOYSA-N Ethyl urethane Chemical compound CCOC(N)=O JOYRKODLDBILNP-UHFFFAOYSA-N 0.000 description 2
- OAKJQQAXSVQMHS-UHFFFAOYSA-N Hydrazine Chemical compound NN OAKJQQAXSVQMHS-UHFFFAOYSA-N 0.000 description 2
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 2
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 2
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 description 2
- 239000004698 Polyethylene Substances 0.000 description 2
- 239000004793 Polystyrene Substances 0.000 description 2
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 2
- 150000001252 acrylic acid derivatives Chemical class 0.000 description 2
- 125000005073 adamantyl group Chemical group C12(CC3CC(CC(C1)C3)C2)* 0.000 description 2
- ISAOCJYIOMOJEB-UHFFFAOYSA-N benzoin Chemical compound C=1C=CC=CC=1C(O)C(=O)C1=CC=CC=C1 ISAOCJYIOMOJEB-UHFFFAOYSA-N 0.000 description 2
- 125000002619 bicyclic group Chemical group 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- WERYXYBDKMZEQL-UHFFFAOYSA-N butane-1,4-diol Chemical compound OCCCCO WERYXYBDKMZEQL-UHFFFAOYSA-N 0.000 description 2
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 239000000470 constituent Substances 0.000 description 2
- 238000005520 cutting process Methods 0.000 description 2
- JHIVVAPYMSGYDF-UHFFFAOYSA-N cyclohexanone Chemical compound O=C1CCCCC1 JHIVVAPYMSGYDF-UHFFFAOYSA-N 0.000 description 2
- 125000000113 cyclohexyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C1([H])[H] 0.000 description 2
- ZQMIGQNCOMNODD-UHFFFAOYSA-N diacetyl peroxide Chemical compound CC(=O)OOC(C)=O ZQMIGQNCOMNODD-UHFFFAOYSA-N 0.000 description 2
- VFHVQBAGLAREND-UHFFFAOYSA-N diphenylphosphoryl-(2,4,6-trimethylphenyl)methanone Chemical compound CC1=CC(C)=CC(C)=C1C(=O)P(=O)(C=1C=CC=CC=1)C1=CC=CC=C1 VFHVQBAGLAREND-UHFFFAOYSA-N 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 229920001971 elastomer Polymers 0.000 description 2
- 239000000839 emulsion Substances 0.000 description 2
- 230000001747 exhibiting effect Effects 0.000 description 2
- 125000000524 functional group Chemical group 0.000 description 2
- 230000004927 fusion Effects 0.000 description 2
- HJOVHMDZYOCNQW-UHFFFAOYSA-N isophorone Chemical compound CC1=CC(=O)CC(C)(C)C1 HJOVHMDZYOCNQW-UHFFFAOYSA-N 0.000 description 2
- 239000012528 membrane Substances 0.000 description 2
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 description 2
- 229910052753 mercury Inorganic materials 0.000 description 2
- BHIWKHZACMWKOJ-UHFFFAOYSA-N methyl isobutyrate Chemical compound COC(=O)C(C)C BHIWKHZACMWKOJ-UHFFFAOYSA-N 0.000 description 2
- 125000004108 n-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 2
- SLCVBVWXLSEKPL-UHFFFAOYSA-N neopentyl glycol Chemical compound OCC(C)(C)CO SLCVBVWXLSEKPL-UHFFFAOYSA-N 0.000 description 2
- 150000001451 organic peroxides Chemical class 0.000 description 2
- WXZMFSXDPGVJKK-UHFFFAOYSA-N pentaerythritol Chemical compound OCC(CO)(CO)CO WXZMFSXDPGVJKK-UHFFFAOYSA-N 0.000 description 2
- XNLICIUVMPYHGG-UHFFFAOYSA-N pentan-2-one Chemical compound CCCC(C)=O XNLICIUVMPYHGG-UHFFFAOYSA-N 0.000 description 2
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- 239000003505 polymerization initiator Substances 0.000 description 2
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- 229920002223 polystyrene Polymers 0.000 description 2
- 229920001289 polyvinyl ether Polymers 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- 230000002829 reductive effect Effects 0.000 description 2
- 239000005060 rubber Substances 0.000 description 2
- 239000013464 silicone adhesive Substances 0.000 description 2
- 239000000758 substrate Substances 0.000 description 2
- DGVVWUTYPXICAM-UHFFFAOYSA-N β‐Mercaptoethanol Chemical compound OCCS DGVVWUTYPXICAM-UHFFFAOYSA-N 0.000 description 2
- FBOUIAKEJMZPQG-AWNIVKPZSA-N (1E)-1-(2,4-dichlorophenyl)-4,4-dimethyl-2-(1,2,4-triazol-1-yl)pent-1-en-3-ol Chemical compound C1=NC=NN1/C(C(O)C(C)(C)C)=C/C1=CC=C(Cl)C=C1Cl FBOUIAKEJMZPQG-AWNIVKPZSA-N 0.000 description 1
- RLUFBDIRFJGKLY-UHFFFAOYSA-N (2,3-dichlorophenyl)-phenylmethanone Chemical compound ClC1=CC=CC(C(=O)C=2C=CC=CC=2)=C1Cl RLUFBDIRFJGKLY-UHFFFAOYSA-N 0.000 description 1
- HGXJDMCMYLEZMJ-UHFFFAOYSA-N (2-methylpropan-2-yl)oxy 2,2-dimethylpropaneperoxoate Chemical compound CC(C)(C)OOOC(=O)C(C)(C)C HGXJDMCMYLEZMJ-UHFFFAOYSA-N 0.000 description 1
- 229920003067 (meth)acrylic acid ester copolymer Polymers 0.000 description 1
- XKSUVRWJZCEYQQ-UHFFFAOYSA-N 1,1-dimethoxyethylbenzene Chemical compound COC(C)(OC)C1=CC=CC=C1 XKSUVRWJZCEYQQ-UHFFFAOYSA-N 0.000 description 1
- FKTHNVSLHLHISI-UHFFFAOYSA-N 1,2-bis(isocyanatomethyl)benzene Chemical compound O=C=NCC1=CC=CC=C1CN=C=O FKTHNVSLHLHISI-UHFFFAOYSA-N 0.000 description 1
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- DKEGCUDAFWNSSO-UHFFFAOYSA-N 1,8-dibromooctane Chemical compound BrCCCCCCCCBr DKEGCUDAFWNSSO-UHFFFAOYSA-N 0.000 description 1
- SCMVPOVMOHQFKU-UHFFFAOYSA-N 1-(aziridin-1-yl)prop-2-en-1-one Chemical compound C=CC(=O)N1CC1 SCMVPOVMOHQFKU-UHFFFAOYSA-N 0.000 description 1
- OSSNTDFYBPYIEC-UHFFFAOYSA-N 1-ethenylimidazole Chemical compound C=CN1C=CN=C1 OSSNTDFYBPYIEC-UHFFFAOYSA-N 0.000 description 1
- 239000012956 1-hydroxycyclohexylphenyl-ketone Substances 0.000 description 1
- RESPXSHDJQUNTN-UHFFFAOYSA-N 1-piperidin-1-ylprop-2-en-1-one Chemical compound C=CC(=O)N1CCCCC1 RESPXSHDJQUNTN-UHFFFAOYSA-N 0.000 description 1
- DGPVNNMFVYYVDF-UHFFFAOYSA-N 1-prop-2-enoylpyrrolidin-2-one Chemical compound C=CC(=O)N1CCCC1=O DGPVNNMFVYYVDF-UHFFFAOYSA-N 0.000 description 1
- WLPAQAXAZQUXBG-UHFFFAOYSA-N 1-pyrrolidin-1-ylprop-2-en-1-one Chemical compound C=CC(=O)N1CCCC1 WLPAQAXAZQUXBG-UHFFFAOYSA-N 0.000 description 1
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- CZZVAVMGKRNEAT-UHFFFAOYSA-N 2,2-dimethylpropane-1,3-diol;3-hydroxy-2,2-dimethylpropanoic acid Chemical compound OCC(C)(C)CO.OCC(C)(C)C(O)=O CZZVAVMGKRNEAT-UHFFFAOYSA-N 0.000 description 1
- YRTNMMLRBJMGJJ-UHFFFAOYSA-N 2,2-dimethylpropane-1,3-diol;hexanedioic acid Chemical compound OCC(C)(C)CO.OC(=O)CCCCC(O)=O YRTNMMLRBJMGJJ-UHFFFAOYSA-N 0.000 description 1
- BTJPUDCSZVCXFQ-UHFFFAOYSA-N 2,4-diethylthioxanthen-9-one Chemical compound C1=CC=C2C(=O)C3=CC(CC)=CC(CC)=C3SC2=C1 BTJPUDCSZVCXFQ-UHFFFAOYSA-N 0.000 description 1
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- XOGPDSATLSAZEK-UHFFFAOYSA-N 2-Aminoanthraquinone Chemical compound C1=CC=C2C(=O)C3=CC(N)=CC=C3C(=O)C2=C1 XOGPDSATLSAZEK-UHFFFAOYSA-N 0.000 description 1
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- DZZAHLOABNWIFA-UHFFFAOYSA-N 2-butoxy-1,2-diphenylethanone Chemical compound C=1C=CC=CC=1C(OCCCC)C(=O)C1=CC=CC=C1 DZZAHLOABNWIFA-UHFFFAOYSA-N 0.000 description 1
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- KMNCBSZOIQAUFX-UHFFFAOYSA-N 2-ethoxy-1,2-diphenylethanone Chemical compound C=1C=CC=CC=1C(OCC)C(=O)C1=CC=CC=C1 KMNCBSZOIQAUFX-UHFFFAOYSA-N 0.000 description 1
- VGZZAZYCLRYTNQ-UHFFFAOYSA-N 2-ethoxyethoxycarbonyloxy 2-ethoxyethyl carbonate Chemical compound CCOCCOC(=O)OOC(=O)OCCOCC VGZZAZYCLRYTNQ-UHFFFAOYSA-N 0.000 description 1
- SJEBAWHUJDUKQK-UHFFFAOYSA-N 2-ethylanthraquinone Chemical compound C1=CC=C2C(=O)C3=CC(CC)=CC=C3C(=O)C2=C1 SJEBAWHUJDUKQK-UHFFFAOYSA-N 0.000 description 1
- YJQMXVDKXSQCDI-UHFFFAOYSA-N 2-ethylthioxanthen-9-one Chemical compound C1=CC=C2C(=O)C3=CC(CC)=CC=C3SC2=C1 YJQMXVDKXSQCDI-UHFFFAOYSA-N 0.000 description 1
- XMLYCEVDHLAQEL-UHFFFAOYSA-N 2-hydroxy-2-methyl-1-phenylpropan-1-one Chemical compound CC(C)(O)C(=O)C1=CC=CC=C1 XMLYCEVDHLAQEL-UHFFFAOYSA-N 0.000 description 1
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Images
Classifications
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J7/00—Adhesives in the form of films or foils
- C09J7/20—Adhesives in the form of films or foils characterised by their carriers
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B7/00—Layered products characterised by the relation between layers; Layered products characterised by the relative orientation of features between layers, or by the relative values of a measurable parameter between layers, i.e. products comprising layers having different physical, chemical or physicochemical properties; Layered products characterised by the interconnection of layers
- B32B7/04—Interconnection of layers
- B32B7/12—Interconnection of layers using interposed adhesives or interposed materials with bonding properties
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B65—CONVEYING; PACKING; STORING; HANDLING THIN OR FILAMENTARY MATERIAL
- B65H—HANDLING THIN OR FILAMENTARY MATERIAL, e.g. SHEETS, WEBS, CABLES
- B65H2701/00—Handled material; Storage means
- B65H2701/10—Handled articles or webs
- B65H2701/17—Nature of material
- B65H2701/172—Composite material
- B65H2701/1722—Composite material including layer with adhesive properties
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B65—CONVEYING; PACKING; STORING; HANDLING THIN OR FILAMENTARY MATERIAL
- B65H—HANDLING THIN OR FILAMENTARY MATERIAL, e.g. SHEETS, WEBS, CABLES
- B65H2701/00—Handled material; Storage means
- B65H2701/10—Handled articles or webs
- B65H2701/17—Nature of material
- B65H2701/175—Plastic
- B65H2701/1752—Polymer film
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J2301/00—Additional features of adhesives in the form of films or foils
- C09J2301/20—Additional features of adhesives in the form of films or foils characterized by the structural features of the adhesive itself
- C09J2301/208—Additional features of adhesives in the form of films or foils characterized by the structural features of the adhesive itself the adhesive layer being constituted by at least two or more adjacent or superposed adhesive layers, e.g. multilayer adhesive
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Adhesive Tapes (AREA)
- Laminated Bodies (AREA)
- Adhesives Or Adhesive Processes (AREA)
Abstract
The invention provides an adhesive sheet winding body, which can wind an adhesive sheet with excellent appearance. The adhesive sheet roll (1) is formed by winding a long adhesive sheet (10) comprising a first film (11), a first adhesive layer (12) laminated on one surface side of the first film (11), and a second film (13) laminated on one side of the first adhesive layer (12) opposite to the first film (11), around a cylindrical or cylindrical core material (20) with the surface on the first film (11) side as the outer side, wherein the diameter of the core material (20) is not less than 180mm and not more than 800mm, and the surface on the first adhesive layer (12) side of the second film (13) is not peeled.
Description
Technical Field
The present invention relates to an adhesive sheet roll, which is obtained by winding an adhesive sheet that includes a first film, a first adhesive layer, and a second film, the second film being not a release sheet, around a core material such that a surface on the first film side is an outer side.
Background
An adhesive sheet having at least an adhesive layer is usually produced in a long form. Further, the adhesive sheet manufactured in a long form as described above is usually manufactured and wound around a core member to be formed into an adhesive sheet roll. The adhesive sheet roll thus produced is also transported and stored in this form.
In addition, when a predetermined product is manufactured, an adhesive sheet may be used as a material or a process sheet, and an apparatus used for the manufacturing is generally used for manufacturing the product while unwinding the adhesive sheet from the adhesive sheet roll as described above.
As an example of manufacturing a predetermined product using an adhesive sheet roll, patent document 1 discloses a method of manufacturing an optical display device by unwinding a predetermined amount of a film from a roll-shaped material including a polarizing plate including a polarizing film and a polarizer protective film, an adhesive layer, and a release film.
Documents of the prior art
Patent document
Patent document 1: japanese patent No. 5801027
Disclosure of Invention
Technical problem to be solved by the invention
However, in the wound adhesive sheet, there is a problem in appearance such that many wrinkles are generated in the unwound adhesive sheet. Such a problem in appearance of the adhesive sheet may not only impair the appearance of a product obtained by using the adhesive sheet, but also adversely affect the performance of the product.
The present invention has been made in view of the above circumstances, and an object thereof is to provide an adhesive sheet roll that can unwind an adhesive sheet having an excellent appearance.
Means for solving the problems
In order to achieve the above object, a first aspect of the present invention provides an adhesive sheet roll comprising a cylindrical or cylindrical core material, a first film, a first adhesive layer laminated on one surface of the first film, and a second film laminated on the first adhesive layer on the side opposite to the first film, the adhesive sheet roll being characterized in that the core material has a diameter of 180mm or more and 800mm or less, and the surface of the second film on the first adhesive layer side is not subjected to a peeling treatment (invention 1).
In the pressure-sensitive adhesive sheet roll of the invention (invention 1), the pressure-sensitive adhesive sheet wound around the core member having the above diameter can be unwound to suppress the occurrence of wrinkles and to provide a pressure-sensitive adhesive sheet having a good appearance.
In the above invention (invention 1), it is preferable that the thickness of the first film is equal to or less than the thickness of the second film (invention 2).
In the above-described inventions (inventions 1 and 2), it is preferable that a peeling force when peeling the first film from a laminate of the first adhesive agent layer and the second film is 10mN/25mm or more and 2000mN/25mm or less (invention 3).
In the above invention (inventions 1 to 3), the adhesive sheet preferably includes: a second adhesive layer laminated on one side of the second film opposite to the first adhesive layer; and a third film laminated on the second adhesive layer on the side opposite to the second film (invention 4).
In the invention (invention 4) described above, the adhesion of the laminate of the third film and the second adhesive layer to soda-lime glass is preferably 0.01N/25mm or more and 20N/25mm or less (invention 5).
In the above inventions (inventions 1 to 5), it is preferable that the first adhesive agent layer has a storage modulus at 23 ℃ of 0.001MPa or more and 1.00MPa or less (invention 6).
Effects of the invention
According to the adhesive sheet roll of the present invention, an adhesive sheet having an excellent appearance can be unwound.
Drawings
Fig. 1 is a perspective view of an adhesive sheet roll according to an embodiment of the present invention.
Fig. 2 is a sectional view of an adhesive sheet constituting an adhesive sheet roll according to an embodiment of the present invention.
Description of the reference numerals
1: an adhesive sheet roll; 10: an adhesive sheet; 11: a first film; 12: a first adhesive layer; 13: a second film; 14: a second adhesive layer; 15: a third film; 20: a core material.
Detailed Description
Hereinafter, embodiments of the present invention will be described.
Fig. 1 is a perspective view of an adhesive sheet roll according to an embodiment of the present invention. As shown in fig. 1, the adhesive sheet roll 1 of the present embodiment is formed by winding an elongated adhesive sheet 10 around a cylindrical or cylindrical core member 20.
Fig. 2 is a cross-sectional view of the adhesive sheet 10 of the present embodiment. The adhesive sheet 10 of the present embodiment includes a first film 11, a first adhesive layer 12 laminated on one surface side of the first film 11, and a second film 13 laminated on the opposite surface side of the first adhesive layer 12 from the first film 11. As shown in fig. 2, the adhesive sheet 10 of the present embodiment preferably further includes a second adhesive layer 14 laminated on the side of the second film 13 opposite to the first adhesive layer 12, and a third film 15 laminated on the side of the second adhesive layer 14 opposite to the second film 13.
The adhesive sheet roll 1 of the present embodiment is formed by winding the adhesive sheet 10 around the core 20 with the surface on the first film 11 side being the outer side. The surface of the second film 13 on the first adhesive layer 12 side is not subjected to a peeling treatment. That is, in the pressure-sensitive adhesive sheet roll 1 of the present embodiment, the second film 13 is not a release sheet.
In the adhesive sheet roll 1 of the present embodiment, the diameter of the core material 20 is 180mm to 800 mm. As described above, in the adhesive sheet roll 1 of the present embodiment, since the adhesive sheet 10 is wound around the core member 20 having a large diameter, the adhesive sheet 10 in which the occurrence of wrinkles is suppressed can be unwound. That is, according to the adhesive sheet roll 1 of the present embodiment, the adhesive sheet 10 having a good appearance can be unwound. In the present specification, when the core 20 has a cylindrical shape, the diameter of the core 20 refers to the outer diameter of the cylinder.
In the present specification, the wrinkle generated in the adhesive sheet unwound from the adhesive sheet roll means any of a deformed wrinkle (distortion みシワ) generated by at least partial deformation of the adhesive sheet and a fold (fold れシワ) generated by bending the adhesive sheet.
It is also presumed that the wrinkles are generally generated on the second film located inside the roll during the production of the roll of adhesive sheet or during storage thereafter, and also propagate to the first adhesive layer. However, when the adhesive sheet is unwound from the adhesive sheet roll, the second film tends to have wrinkles removed because the unwinding tension is applied to the second film and the film restoring force is large. In contrast, wrinkles in the first adhesive layer do not disappear by unwinding, and easily remain on the unwound adhesive sheet. The adhesive sheet roll 1 of the present embodiment can satisfactorily suppress the occurrence of wrinkles occurring in the adhesive sheet 10 including such wrinkles remaining in the first adhesive layer.
The use form of the adhesive sheet 10 of the present embodiment is not limited, and the following use forms can be typically cited. First, the first film 11 is peeled and removed from the adhesive sheet 10 unwound from the adhesive sheet roll 1. Then, the laminate of the second film 13 and the first adhesive layer 12 thus obtained was attached to an adherend on the surface on the first adhesive layer 12 side. When the adhesive sheet 10 includes the second adhesive layer 14 and the third film 15, a laminated body of the second adhesive layer 14 and the third film 15 can be used as a protective film for protecting the second film 13. Such a protective film can be peeled off from the second film 13 at any timing.
1. Structure of adhesive sheet roll
(1) First film
In the pressure-sensitive adhesive sheet roll 1 of the present embodiment, the material of the first film 11 is not particularly limited. For example, the first film 11 may be made of a resin sheet mainly composed of a resin material, or may be made of a paper material.
Examples of the resin component of the resin sheet include polyolefins such as polyethylene, polypropylene, polybutylene, polybutadiene, polymethylpentene, an ethylene-norbornene copolymer, and a norbornene resin, polyesters such as polyethylene terephthalate, polyethylene naphthalate, and polybutylene terephthalate, polyvinyl chloride, a vinyl chloride copolymer, polyimide, polyetherimide, polycarbonate, polyphenylene sulfide, and a liquid crystal polymer. These resin sheets may be sheets each composed of a single layer, or sheets each obtained by laminating a plurality of layers of the same type or different types. Among the above, a polyethylene terephthalate film is preferable.
Specific examples of the case where the first film 11 is made of a paper material include paper substrates such as cellophane, coated paper, and fine paper, and laminated paper obtained by laminating a thermoplastic resin such as polyethylene on the paper substrate.
The first film 11 is preferably a release sheet obtained by applying a release treatment to one surface (particularly, the surface in contact with the first adhesive layer 12) of a sheet made of the resin sheet or the paper material. Examples of the release agent used for the release treatment include alkyd based, silicone based, fluorine based, unsaturated polyester based, polyolefin based, and wax based release agents.
The thickness of the first film 11 of the pressure-sensitive adhesive sheet roll 1 of the present embodiment is preferably equal to or less than the thickness of the second film 13. In this way, by making the thickness of the first film 11 located on the outer side of winding the same as or thinner than the thickness of the second film 13 located on the inner side of winding, the winding pressure applied to the second film 13 is easily relaxed. As a result, the occurrence of wrinkles (particularly, the occurrence of wrinkles in the second film 13) can be effectively suppressed in the adhesive sheet 10 unwound from the adhesive sheet roll 1.
From the viewpoint of easily achieving the above-described thickness relationship between the first film 11 and the second film 13, the thickness of the first film 11 is preferably 20 μm or more, particularly preferably 30 μm or more, and more preferably 40 μm or more. The thickness of the first film 11 is preferably 150 μm or less, more preferably 100 μm or less, particularly preferably 80 μm or less, and further preferably 70 μm or less.
The Young's modulus at 23 ℃ of the first film 11 is preferably 0.01GPa or more, more preferably 0.1GPa or more, particularly preferably 1GPa or more, and even more preferably 3GPa or more. The Young's modulus is preferably 20GPa or less, particularly preferably 10GPa or less, and further preferably 5GPa or less. When the young's modulus at 23 ℃ of the first film 11 is 0.01GPa or more, the first film 11 has a predetermined strength, and the adhesive sheet 10 is more excellent in handling properties. Further, by setting the young's modulus at 23 ℃ of the first film 11 to 20GPa or less, the winding pressure of the first film 11 against the second film 13 during winding is reduced, and the generation of wrinkles in the adhesive sheet 10 is more easily suppressed. The young's modulus in the present specification is defined as JIS K7161: 2014, more specifically, a value measured at a tensile rate of 200 mm/min in an environment of 23 ℃ and 50% RH using a universal tensile tester.
(2) A first adhesive layer
The adhesive constituting the first adhesive layer 12 in the present embodiment is not particularly limited as long as it can achieve a desired adhesive force, and may be appropriately selected according to the application. For example, the adhesive constituting the first adhesive layer 12 may be any of an acrylic adhesive, a silicone adhesive, a rubber adhesive, a urethane adhesive, a polyester adhesive, a polyvinyl ether adhesive, and the like. The adhesive may be any of emulsion type, solvent type, and non-solvent type, and may be any of crosslinking type and non-crosslinking type. Among them, an acrylic adhesive is preferably used as the adhesive constituting the first adhesive layer 12 in the present embodiment from the viewpoint of having sufficient transparency and easily exhibiting a desired adhesive force.
The adhesive constituting the first adhesive layer 12 may be an active energy ray-curable adhesive or an inactive energy ray-curable adhesive. The active energy ray-curable adhesive is an adhesive having an active energy ray-curable property in a stage of being used as an adhesive (for example, a stage of attaching an adhesive layer made of the adhesive to an adherend). In the present embodiment, the case where the first adhesive layer 12 has active energy ray curability in the state of the adhesive sheet roll 1 is referred to. The active energy ray-curable adhesive is a concept including an adhesive in a so-called semi-cured (B-stage) state in which active energy ray curing is optionally performed in a stage of producing the adhesive.
On the other hand, an active energy ray-curable adhesive is an adhesive in which the active energy ray curing is completed and the active energy ray-curing property is lost at the stage of being used as an adhesive, or an adhesive which does not have the active energy ray-curing property from the beginning.
Among them, the adhesive layer of the active energy ray-curable adhesive is often lower in cohesive force and more flexible than the non-active energy ray-curable adhesive. Therefore, the active energy ray-curable adhesive tends to have low resistance to deformation of the second film 13 and to easily form wrinkles when the roll is produced. Even when such an adhesive having a high difficulty in suppressing wrinkles is used, the generation of wrinkles can be sufficiently suppressed in the adhesive sheet roll 1 of the present embodiment.
Further, by using an active energy ray-curable adhesive, the adhesive sheet 10 of the present embodiment is suitable for being attached to an adherend having a level difference on the surface. That is, the adhesive sheet 10 of the present embodiment can attach the first adhesive layer 12 to an adherend in a relatively soft state having active energy ray curability, and allow the first adhesive layer 12 to favorably follow a step difference. Then, the cohesive force of the first adhesive agent layer 12 can be sufficiently increased by performing active energy ray curing. Thus, even when the adhesive sheet 10 is left under high-temperature and high-humidity conditions with the cured first adhesive layer 12 attached to an adherend, the occurrence of bubbles, floating, peeling, and the like in the vicinity of the level difference can be favorably suppressed.
Hereinafter, a case where the first adhesive layer 12 of the present embodiment is composed of an active energy ray-curable acrylic adhesive will be described. The first adhesive layer 12 can be formed of, for example, an adhesive obtained by crosslinking (thermally crosslinking) a first adhesive composition (hereinafter, sometimes referred to as "first adhesive composition P1") containing a (meth) acrylate copolymer (a), a crosslinking agent (B), and an active energy ray-curable component (C). The first adhesive composition P1 preferably further contains a photopolymerization initiator (D) as required. In the present specification, (meth) acrylic acid refers to both acrylic acid and methacrylic acid. Other similar terms are also the same. Further, the term "copolymer" is also included in "polymer".
(1-1) (meth) acrylic acid ester copolymer (A)
The (meth) acrylate copolymer (a) preferably contains a reactive group-containing monomer having a reactive group reactive with the crosslinking agent (B) in the molecule as a monomer unit constituting the polymer. Thus, the reactive group derived from the reactive group-containing monomer can react with the crosslinking agent (B). By introducing the monomer into the (meth) acrylate copolymer (a), the gel fraction or storage modulus of the resulting adhesive can be easily adjusted.
Examples of the reactive group-containing monomer include a monomer having a hydroxyl group in the molecule (hydroxyl group-containing monomer), a monomer having a carboxyl group in the molecule (carboxyl group-containing monomer), and a monomer having an amino group in the molecule (amino group-containing monomer). Among these, a hydroxyl group-containing monomer which is excellent in reactivity with the crosslinking agent (B) and has little adverse effect on an adherend is particularly preferable.
Examples of the hydroxyl group-containing monomer include hydroxyalkyl (meth) acrylates such as 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 3-hydroxypropyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate, 3-hydroxybutyl (meth) acrylate, and 4-hydroxybutyl (meth) acrylate. Among these, 2-hydroxyethyl (meth) acrylate and 4-hydroxybutyl (meth) acrylate are preferable from the viewpoint of reactivity of the hydroxyl group in the obtained (meth) acrylate copolymer (a) with the crosslinking agent (B) and copolymerizability with other monomers. The hydroxyl group-containing monomers may be used alone or in combination of two or more.
From the viewpoint of improving the gel fraction or storage modulus of the obtained adhesive to a desired extent, the (meth) acrylate copolymer (a) preferably contains 1 mass% or more, more preferably 5 mass% or more, particularly preferably 10 mass% or more, and further preferably 12 mass% or more of a hydroxyl group-containing monomer as a monomer unit constituting the polymer, in the following limit. From the viewpoint of reducing the gel fraction or storage modulus of the resulting adhesive to a desired extent, the (meth) acrylate copolymer (a) preferably contains 30% by mass or less, particularly preferably 25% by mass or less, and further preferably 20% by mass or less of a hydroxyl group-containing monomer as a monomer unit constituting the polymer.
The (meth) acrylate copolymer (A) can impart a preferable storage modulus to the obtained adhesive and also exhibit preferable tackiness by containing an alkyl (meth) acrylate having 1 to 20 carbon atoms in an alkyl group as a monomer unit constituting the polymer. Examples of the alkyl (meth) acrylate having an alkyl group with 1 to 20 carbon atoms include methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, n-butyl (meth) acrylate, n-pentyl (meth) acrylate, n-hexyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, isooctyl (meth) acrylate, n-decyl (meth) acrylate, n-dodecyl (meth) acrylate, myristyl (meth) acrylate, palmityl (meth) acrylate, and stearyl (meth) acrylate. Among them, from the viewpoint of optimizing the storage modulus and further improving the adhesiveness, a (meth) acrylate having an alkyl group with 4 to 8 carbon atoms is preferable, and 2-ethylhexyl (meth) acrylate is particularly preferable. The alkyl (meth) acrylate may be used singly or in combination of two or more.
The (meth) acrylate copolymer (A) preferably contains at least 40% by mass, particularly preferably at least 50% by mass, and further preferably at least 60% by mass of an alkyl (meth) acrylate having 1 to 20 carbon atoms and an alkyl group as a monomer unit constituting the polymer. The alkyl (meth) acrylate having 1 to 20 carbon atoms preferably contains not more than 90% by mass, particularly preferably not more than 80% by mass, and further preferably not more than 70% by mass of an alkyl group.
It is also preferable that the (meth) acrylate copolymer (a) contains a monomer having an alicyclic structure in the molecule (alicyclic structure-containing monomer) as a monomer unit constituting the copolymer. It is presumed that the alicyclic structure-containing monomer has a large volume, and therefore, when it is present in the polymer, the interval between the polymers can be widened, and the flexibility of the resulting adhesive can be improved. When the (meth) acrylate copolymer (a) contains the alicyclic structure-containing monomer, the first adhesive layer 12 can favorably follow a level difference when the adhesive sheet 10 of the present embodiment is attached to an adherend having the level difference on the surface.
The alicyclic carbon ring in the alicyclic structure-containing monomer may be saturated or partially unsaturated. The alicyclic structure may be a monocyclic alicyclic structure, or may be a polycyclic alicyclic structure such as a bicyclic structure or a tricyclic structure. From the viewpoint of increasing the distance between the obtained (meth) acrylate copolymers (a) and effectively exhibiting flexibility of the adhesive, it is preferable that the alicyclic structure is a polycyclic alicyclic structure (polycyclic structure). Further, in view of compatibility of the (meth) acrylate copolymer (a) with other components, it is particularly preferable that the polycyclic structure is a bicyclic ring to a tetracyclic ring. In addition, from the viewpoint of effectively exerting the same function of the flexibility of the adhesive as described above, the number of carbon atoms of the alicyclic structure (which means the number of all carbon atoms of the portion forming a ring, and when a plurality of rings are present independently, means the total number of carbon atoms thereof) is preferably 5 or more in general, and more preferably 7 or more in particular. On the other hand, the upper limit of the number of carbon atoms of the alicyclic structure is not particularly limited, but from the viewpoint of the same compatibility as described above, it is preferably 15 or less, and particularly preferably 10 or less.
Examples of the alicyclic structure-containing monomer include cyclohexyl (meth) acrylate, dicyclopentanyl (meth) acrylate, adamantyl (meth) acrylate, isobornyl (meth) acrylate, dicyclopentenyl (meth) acrylate, dicyclopentenyloxyethyl (meth) acrylate, and the like, and among them, dicyclopentanyl (meth) acrylate, adamantyl (meth) acrylate, and isobornyl (meth) acrylate which exert more excellent durability are preferable, and isobornyl (meth) acrylate is particularly preferable. The alicyclic structure-containing monomer may be used alone or in combination of two or more.
When the (meth) acrylate copolymer (a) contains an alicyclic structure-containing monomer as a monomer unit constituting the polymer, the (meth) acrylate copolymer (a) preferably contains 3% by mass or more, particularly preferably contains 5% by mass or more, and further preferably contains 8% by mass or more of an alicyclic structure-containing monomer. The (meth) acrylate copolymer (a) preferably contains not more than 35% by mass, particularly preferably not more than 25% by mass, and further preferably not more than 15% by mass of a alicyclic structure-containing monomer as a monomer unit constituting the polymer.
It is also preferable that the (meth) acrylate copolymer (a) contains a monomer having a nitrogen atom in the molecule (nitrogen atom-containing monomer) as a monomer unit constituting the copolymer. In addition, the reactive group-containing monomer is not contained in the nitrogen atom-containing monomer. When a monomer containing a nitrogen atom is present as a structural unit in the polymer, the reaction between the acrylate copolymer (a) and the crosslinking agent (B) can be accelerated, or polarity can be imparted to the adhesive, and the adhesion of the adhesive to a polar surface such as a glass surface can be improved.
Examples of the nitrogen atom-containing monomer include a monomer having a tertiary amino group, a monomer having an amide group, and a monomer having a nitrogen-containing heterocycle, and among them, a monomer having a nitrogen-containing heterocycle is preferable.
Examples of the monomer having a nitrogen-containing heterocycle include N- (meth) acryloylmorpholine, N-vinyl-2-pyrrolidone, N- (meth) acryloylpyrrolidone, N- (meth) acryloylpiperidine, N- (meth) acryloylpyrrolidine, N- (meth) acryloylaziridine, aziridinylethyl (meth) acrylate, 2-vinylpyridine, 4-vinylpyridine, 2-vinylpyrazine, 1-vinylimidazole, N-vinylcarbazole, N-vinylphthalimide and the like, and among them, N- (meth) acryloylmorpholine is preferable from the viewpoint of improving the cohesive force of the resulting adhesive and improving the blister resistance in addition to the adhesion to a polar surface such as a glass surface, n-acryloyl morpholine is particularly preferred.
When the (meth) acrylate copolymer (a) contains a nitrogen atom-containing monomer as a monomer unit constituting the polymer, the (meth) acrylate copolymer (a) preferably contains 1 mass% or more, particularly preferably contains 2 mass% or more, and further preferably contains 5 mass% or more of a nitrogen atom-containing monomer. The (meth) acrylate copolymer (a) preferably contains 40% by mass or less, particularly preferably 25% by mass or less, and further preferably 15% by mass or less of a nitrogen atom-containing monomer as a monomer unit constituting the polymer.
The (meth) acrylate copolymer (a) may contain other monomers as a monomer unit constituting the polymer, as required. As the other monomer, a monomer having no reactive functional group is preferable. Examples of the other monomer include alkoxyalkyl (meth) acrylates such as methoxyethyl (meth) acrylate and ethoxyethyl (meth) acrylate, vinyl acetate, and styrene. The other monomers may be used alone or in combination of two or more.
The polymerization form of the (meth) acrylate copolymer (a) may be a random copolymer or a block copolymer.
The weight average molecular weight of the (meth) acrylate copolymer (a) is preferably 10 ten thousand or more, particularly preferably 20 ten thousand or more, and more preferably 30 ten thousand or more, in the lower limit value. When the lower limit of the weight average molecular weight of the (meth) acrylate copolymer (a) is not less than the above range, the cohesive force of the obtained adhesive can be increased, the storage modulus and gel fraction of the adhesive can be prevented from becoming too low, and the adhesive force can be prevented from becoming too high. The weight average molecular weight of the (meth) acrylate copolymer (a) is preferably 100 ten thousand or less, particularly preferably 85 ten thousand or less, and more preferably 70 ten thousand or less, as defined above. When the upper limit of the weight average molecular weight of the (meth) acrylate copolymer (a) is not more than the above, the storage modulus and gel fraction of the obtained adhesive can be prevented from becoming excessively high, and the adhesive force can be prevented from becoming excessively low. The weight average molecular weight in the present specification is a value in terms of standard polystyrene measured by a Gel Permeation Chromatography (GPC) method.
In the first adhesive composition P1, one kind of the (meth) acrylate copolymer (a) may be used alone, or two or more kinds may be used in combination.
(1-2) crosslinking agent (B)
The crosslinking agent (B) can crosslink the (meth) acrylate copolymer (a) by heating the first adhesive composition P1 to form a three-dimensional network structure well. This further improves the cohesive force of the adhesive, and facilitates adjustment of the gel fraction and the storage modulus to appropriate values.
The crosslinking agent (B) may be reacted with the reactive functional group of the (meth) acrylate copolymer (a), and examples thereof include isocyanate crosslinking agents, epoxy crosslinking agents, amine crosslinking agents, melamine crosslinking agents, aziridine crosslinking agents, hydrazine crosslinking agents, aldehyde crosslinking agents, oxazoline crosslinking agents, metal alkoxide crosslinking agents, metal chelate crosslinking agents, metal salt crosslinking agents, and ammonium salt crosslinking agents. Here, as described above, since the (meth) acrylate copolymer (a) preferably contains a hydroxyl group-containing monomer as a constituent monomer unit, an isocyanate-based crosslinking agent having excellent reactivity with a hydroxyl group is preferably used as the crosslinking agent (B). The crosslinking agent (B) may be used alone or in combination of two or more.
The isocyanate-based crosslinking agent contains at least a polyisocyanate compound. Examples of the polyisocyanate compound include aromatic polyisocyanates such as tolylene diisocyanate, diphenylmethane diisocyanate and xylylene diisocyanate, aliphatic polyisocyanates such as hexamethylene diisocyanate, alicyclic polyisocyanates such as isophorone diisocyanate and hydrogenated diphenylmethane diisocyanate, and biuret and isocyanurate compounds thereof, and further include adducts thereof with a reaction product of a low-molecular active hydrogen-containing compound such as ethylene glycol, propylene glycol, neopentyl glycol, trimethylolpropane and castor oil. Among them, trimethylolpropane-modified aromatic polyisocyanates are preferable from the viewpoint of reactivity with hydroxyl groups, and trimethylolpropane-modified tolylene diisocyanate is particularly preferable.
The content of the crosslinking agent (B) in the first adhesive composition P1 is preferably 0.01 part by mass or more, particularly preferably 0.05 part by mass or more, and more preferably 0.1 part by mass or more, relative to 100 parts by mass of the (meth) acrylate copolymer (a). The content is preferably 3 parts by mass or less, particularly preferably 2 parts by mass or less, and more preferably 1 part by mass or less, relative to 100 parts by mass of the (meth) acrylate copolymer (a). When the content of the crosslinking agent (B) is within the above range, the gel fraction and the storage modulus of the obtained adhesive can be easily adjusted to appropriate values.
(1-3) active energy ray-curable component (C)
The adhesive obtained by crosslinking (thermally crosslinking) the first adhesive composition P1 by including the active energy ray-curable component (C) in the first adhesive composition P1 becomes an active energy ray-curable adhesive. It is presumed that the active energy ray-curable component (C) is mutually polymerized by curing by irradiation with active energy rays after the adherend is attached to the adhesive, and the active energy ray-curable component (C) after the polymerization is entangled with the crosslinked structure (three-dimensional network structure) of the (meth) acrylate copolymer (a). By forming the high-dimensional structure, the gel fraction and the storage modulus are easily increased, and the anchoring effect and the adhesion are easily increased.
The active energy ray-curable component (C) is not particularly limited as long as it is cured by irradiation with an active energy ray and can obtain the above-described effects, and may be any of a monomer, an oligomer, or a polymer, or a mixture thereof. Among them, preferred are polyfunctional acrylate monomers having excellent compatibility with the (meth) acrylate copolymer (a) and the like.
Examples of the polyfunctional acrylate monomer include 1, 4-butanediol di (meth) acrylate, 1, 6-hexanediol di (meth) acrylate, neopentyl glycol di (meth) acrylate, polyethylene glycol di (meth) acrylate, neopentyl glycol adipate di (meth) acrylate, hydroxypivalic acid neopentyl glycol di (meth) acrylate, dicyclopentyl di (meth) acrylate, bifunctional types such as caprolactone-modified dicyclopentenyl di (meth) acrylate, ethylene oxide-modified phosphoric acid di (meth) acrylate, di (acryloyloxyethyl) isocyanurate, allylated cyclohexyl di (meth) acrylate, ethoxylated bisphenol a diacrylate, and 9, 9-bis [4- (2-acryloyloxyethoxy) phenyl ] fluorene; trifunctional types such as trimethylolpropane tri (meth) acrylate, dipentaerythritol tri (meth) acrylate, propionic acid-modified dipentaerythritol tri (meth) acrylate, pentaerythritol tri (meth) acrylate, propylene oxide-modified trimethylolpropane tri (meth) acrylate, tris (acryloyloxyethyl) isocyanurate, and e-caprolactone-modified tris (2- (meth) acryloyloxyethyl) isocyanurate; tetrafunctional types such as diglycerin tetra (meth) acrylate and pentaerythritol tetra (meth) acrylate; pentafunctional types such as propionic acid-modified dipentaerythritol penta (meth) acrylate; and hexa-functional types such as dipentaerythritol hexa (meth) acrylate and caprolactone-modified dipentaerythritol hexa (meth) acrylate. Among the above, from the viewpoint of poor followability under high-temperature and high-humidity conditions of the obtained adhesive, polyfunctional acrylate monomers having an isocyanurate structure in the molecule, such as bis (acryloyloxyethyl) isocyanurate, tris (acryloyloxyethyl) isocyanurate, and e-caprolactone-modified tris- (2- (meth) acryloyloxyethyl) isocyanurate, are preferable, and polyfunctional acrylate monomers having a trifunctional or higher functionality and an isocyanurate structure in the molecule are more preferable. The polyfunctional acrylate monomer may be used alone or in combination of two or more. In addition, from the viewpoint of compatibility with the (meth) acrylate copolymer (a), the molecular weight of the polyfunctional acrylate monomer is preferably less than 1000.
From the viewpoint of facilitating the increase in gel fraction and storage modulus, the content of the active energy ray-curable component (C) in the first adhesive composition P1 is preferably 1 part by mass or more, more preferably 3 parts by mass or more, and particularly preferably 5 parts by mass or more, based on 100 parts by mass of the (meth) acrylate copolymer (a), as the lower limit. The content is preferably 50 parts by mass or less, more preferably 20 parts by mass or less, and particularly preferably 10 parts by mass or less, based on 100 parts by mass of the (meth) acrylate copolymer (a).
(1-4) photopolymerization initiator (D)
When ultraviolet rays are used as the active energy rays for curing the active energy ray-curable adhesive, the first adhesive composition P1 preferably further contains a photopolymerization initiator (D). By containing the photopolymerization initiator (D) as described above, the active energy ray-curable component (C) can be efficiently polymerized, and the polymerization curing time and the irradiation dose of the active energy ray can be reduced.
Examples of the photopolymerization initiator (D) include benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, benzoin n-butyl ether, benzoin isobutyl ether, acetophenone, dimethylaminoacetophenone, 2-dimethoxy-2-phenylacetophenone, 2-diethoxy-2-phenylacetophenone, 2-hydroxy-2-methyl-1-phenylpropan-1-one, 1-hydroxycyclohexylphenyl ketone, 2-methyl-1- [4- (methylthio) phenyl ] -2-morpholinyl-propan-1-one, 4- (2-hydroxyethoxy) phenyl-2- (hydroxy-2-propyl) ketone, benzophenone, and the like, P-phenylbenzophenone, 4' -diethylaminobenzophenone, dichlorobenzophenone, 2-methylanthraquinone, 2-ethylanthraquinone, 2-tert-butylanthraquinone, 2-aminoanthraquinone, 2-methylthioxanthone, 2-ethylthioxanthone, 2-chlorothioxanthone, 2, 4-dimethylthioxanthone, 2, 4-diethylthioxanthone, benzildimethylketal, acetophenone dimethylketal, p-dimethylaminobenzoate, oligo [ 2-hydroxy-2-methyl-1 [4- (1-methylvinyl) phenyl ] acetone ], 2,4, 6-trimethylbenzoyl-diphenyl-phosphine oxide, and the like. Among these, a phosphine oxide-based photopolymerization initiator is more preferably used because a sufficient curing reaction can be performed through the ultraviolet absorber-containing resin sheet. The photopolymerization initiators may be used alone or in combination of two or more.
The content of the photopolymerization initiator (D) in the first adhesive composition P1 is preferably 0.1 part by mass or more, and particularly preferably 1 part by mass or more, with respect to 100 parts by mass of the active energy ray-curable component (C), as the lower limit value. The content is preferably 30 parts by mass or less, and particularly preferably 15 parts by mass or less.
(1-5) various additives
Various additives commonly used for acrylic adhesives, such as silane coupling agents, ultraviolet absorbers, antistatic agents, tackifiers, antioxidants, light stabilizers, softeners, fillers, refractive index modifiers, and the like, may be added to the first adhesive composition P1 as needed. The polymerization solvent or the dilution solvent described later is not included in the additive constituting the first adhesive composition P1.
Here, when the first adhesive composition P1 contains a silane coupling agent, the adhesion of the obtained adhesive to a glass member or a plastic plate is improved.
The silane coupling agent is preferably an organosilicon compound having at least one alkoxysilyl group in the molecule, good compatibility with the (meth) acrylate copolymer (a), and light transmittance.
Examples of the silane coupling agent include silicon compounds containing a polymerizable unsaturated group such as vinyltrimethoxysilane, vinyltriethoxysilane, and methacryloxypropyltrimethoxysilane; silicon compounds having an epoxy structure such as 3-glycidoxypropyltrimethoxysilane and 2- (3, 4-epoxycyclohexyl) ethyltrimethoxysilane; mercapto group-containing silicon compounds such as 3-mercaptopropyltrimethoxysilane, 3-mercaptopropyltriethoxysilane, 3-mercaptopropyldimethoxymethylsilane, etc.; amino group-containing silicon compounds such as 3-aminopropyltrimethoxysilane, N- (2-aminoethyl) -3-aminopropyltrimethoxysilane and N- (2-aminoethyl) -3-aminopropylmethyldimethoxysilane; 3-chloropropyltrimethoxysilane; isocyanatopropyltriethoxysilane; or condensates of at least one of these silane coupling agents with an alkyl group-containing silicon compound such as methyltriethoxysilane, ethyltriethoxysilane, methyltrimethoxysilane, ethyltrimethoxysilane, or the like. The silane coupling agent may be used alone or in combination of two or more.
When the first adhesive composition P1 contains a silane coupling agent, the content thereof is preferably 0.01 parts by mass or more, particularly preferably 0.05 parts by mass or more, and more preferably 0.1 parts by mass or more, per 100 parts by mass of the (meth) acrylate copolymer (a). The content is preferably 2 parts by mass or less, particularly preferably 1 part by mass or less, and more preferably 0.5 part by mass or less, relative to 100 parts by mass of the (meth) acrylate copolymer (a).
(1-6) preparation of first adhesive composition
The first adhesive composition P1 can be prepared by: the (meth) acrylate copolymer (a) is prepared, and the obtained (meth) acrylate copolymer (a), the crosslinking agent (B), the active energy ray-curable component (C), the photopolymerization initiator (D), and additives are mixed as needed.
The (meth) acrylate copolymer (a) can be prepared by polymerizing a mixture of monomers constituting the polymer by a general radical polymerization method. The polymerization of the (meth) acrylate copolymer (a) is preferably carried out by a solution polymerization method using a polymerization initiator as needed. Examples of the polymerization solvent include ethyl acetate, n-butyl acetate, isobutyl acetate, toluene, acetone, hexane, and methyl ethyl ketone, and two or more of them may be used simultaneously.
Examples of the polymerization initiator include azo compounds and organic peroxides, and two or more of them may be used simultaneously. Examples of the azo compound include 2,2 ' -azobisisobutyronitrile, 2 ' -azobis (2-methylbutyronitrile), 1 ' -azobis (cyclohexane 1-carbonitrile), 2 ' -azobis (2, 4-dimethylvaleronitrile), 2 ' -azobis (2, 4-dimethyl-4-methoxyvaleronitrile), 2 ' -azobis (methyl 2-methylpropionate), 4 ' -azobis (4-cyanovaleric acid), 2 ' -azobis (2-hydroxymethylpropionitrile), and 2,2 ' -azobis [2- (2-imidazolin-2-yl) propane ].
Examples of the organic peroxide include benzoyl peroxide, tert-butyl peroxybenzoate, cumene hydroperoxide, diisopropyl peroxydicarbonate, di-n-propyl peroxydicarbonate, di (2-ethoxyethyl) peroxydicarbonate, tert-butyl peroxyneodecanoate, tert-butyl peroxypivalate, 3,5, 5-trimethylhexanoyl peroxide, dipropionyl peroxide, and diacetyl peroxide.
In the polymerization step, a chain transfer agent such as 2-mercaptoethanol is added to adjust the weight average molecular weight of the obtained polymer.
After the (meth) acrylate copolymer (a) is obtained, the crosslinking agent (B), the active energy ray-curable component (C), the photopolymerization initiator (D), the additive, and the diluting solvent are added to a solution of the (meth) acrylate copolymer (a) as needed, and sufficiently mixed, whereby the first adhesive composition P1 (coating solution) diluted with the solvent can be obtained. In addition, when a solid component is used or when the component is precipitated when the component is mixed with another component in an undiluted state, the component may be dissolved or diluted in a diluting solvent in advance and then mixed with another component.
Examples of the diluting solvent include aliphatic hydrocarbons such as hexane, heptane and cyclohexane; aromatic hydrocarbons such as toluene and xylene; halogenated hydrocarbons such as dichloromethane and vinyl chloride; alcohols such as methanol, ethanol, propanol, butanol, and 1-methoxy-2-propanol; ketones such as acetone, methyl ethyl ketone, 2-pentanone, isophorone, and cyclohexanone; esters such as ethyl acetate and butyl acetate; and cellosolve solvents such as ethyl cellosolve.
The concentration and viscosity of the coating solution prepared in the above manner are not particularly limited as long as they are within a coatable range, and may be appropriately selected according to circumstances. For example, the first pressure-sensitive adhesive composition P1 is diluted so that the concentration thereof is 10 to 60 mass%. In addition, when obtaining the coating solution, it is not an essential condition to add a dilution solvent, and the dilution solvent may not be added if the first adhesive composition P1 has a coatable viscosity or the like. In this case, the first adhesive composition P1 is a coating solution in which the polymerization solvent of the (meth) acrylate copolymer (a) is used as it is as a dilution solvent.
(1-7) physical Properties of the first adhesive agent layer, etc
The thickness of the first adhesive layer 12 of the present embodiment can be appropriately set according to the use of the adhesive sheet 10. For example, the thickness is preferably 100 μm or more, more preferably 140 μm or more, particularly preferably 180 μm or more, and further preferably 200 μm or more. By setting the thickness of the first adhesive agent layer 12 to 100 μm or more, excellent step following property can be easily achieved. The thickness is preferably 1000 μm or less, particularly preferably 500 μm or less, and more preferably 300 μm or less. By setting the thickness of the first adhesive layer 12 to 1000 μm or less, the occurrence of wrinkles in the adhesive sheet 1 can be easily and effectively suppressed. Further, as the thickness of the first adhesive layer 12 increases, the winding pressure of the first film 11 against the second film 13 due to winding tends to increase, and the difficulty in suppressing wrinkles tends to increase.
From the viewpoint of further reducing the occurrence of wrinkles, the storage modulus at 23 ℃ of the first adhesive agent layer 12 of the present embodiment is preferably 0.001MPa or more, particularly preferably 0.01MPa or more, and more preferably 0.05MPa or more. The storage modulus is preferably 1.00MPa or less, more preferably 0.5MPa or less, particularly preferably 0.2MPa or less, and further preferably 0.09MPa or less. By setting the storage modulus at 23 ℃ of the first adhesive layer 12 to the above upper limit, even when the adhesive sheet 10 of the present embodiment is attached to an adherend having a step difference on the surface, the first adhesive layer 12 more favorably follows the step difference when the attachment is performed. When the first adhesive layer 12 of the present embodiment is composed of the active energy ray-curable adhesive described above, the storage modulus refers to the storage modulus before the first adhesive layer 12 is irradiated with an active energy ray unless otherwise specified. The method for testing the storage modulus is shown in the test examples described below.
When the first adhesive layer 12 of the present embodiment is composed of the active energy ray-curable adhesive, the storage modulus at 23 ℃ of the first adhesive layer 12 after the irradiation of the first adhesive layer 12 with an active energy ray is preferably 0.01MPa or more, particularly preferably 0.06MPa or more, and more preferably 0.11MPa or more. The storage modulus is preferably 2MPa or less, more preferably 1MPa or less, particularly preferably 0.5MPa or less, and further preferably 0.32MPa or less. When the storage modulus at 23 ℃ after irradiation with the active energy ray of the first adhesive agent layer 12 is in the above range, the first adhesive agent layer 12 is more excellent in step following property under durable conditions. The method for testing the storage modulus is shown in the test examples described below.
When the first adhesive layer 12 is formed of an active energy ray-curable adhesive, the ratio of the storage modulus at 23 ℃ of the first adhesive layer 12 after irradiation with an active energy ray to the storage modulus at 23 ℃ of the first adhesive layer 12 before irradiation with an active energy ray is preferably 1.1 times or more, particularly preferably 1.6 times or more, and more particularly preferably 1.9 times or more. On the other hand, the ratio is preferably 10 times or less, more preferably 5 times or less, and still more preferably 3 times or less. When the ratio is in the above range, the first adhesive layer 12 is more excellent in step following property under a durable condition.
The gel fraction of the adhesive constituting the first adhesive layer 12 of the present embodiment is preferably 20% or more, particularly preferably 30% or more, and more preferably 40% or more. The gel fraction is preferably 80% or less, particularly preferably 70% or less, and more preferably 60% or less. When the gel fraction of the adhesive constituting the first adhesive layer 12 is set to the upper limit value, the adhesive has a suitable cohesive force. Thus, even when the adhesive sheet 10 of the present embodiment is attached to an adherend having a step on the surface, the first adhesive layer 12 can more favorably follow the step when the attachment is performed. When the first adhesive layer 12 of the present embodiment is composed of the active energy ray-curable adhesive, the gel fraction refers to the gel fraction before the first adhesive layer 12 is irradiated with an active energy ray unless otherwise specified. The test method of the gel fraction is shown in the test examples described below.
When the first adhesive layer 12 of the present embodiment is composed of the active energy ray-curable adhesive, the gel fraction of the adhesive constituting the first adhesive layer 12 after irradiation of the first adhesive layer 12 with active energy rays is preferably 45% or more, particularly preferably 55% or more, and further preferably 65% or more. The gel fraction is preferably 95% or less, particularly preferably 85% or less, and more preferably 75% or less. When the gel fraction at 23 ℃ after the irradiation with the active energy ray of the first adhesive agent layer 12 is in the above range, the cohesive force of the adhesive after the irradiation with the active energy ray is favorably improved. Thus, the first adhesive layer 12 is more excellent in step following property under durable conditions. The method for testing the storage modulus is shown in the test examples described below.
(3) Second film
In the adhesive sheet roll 1 of the present embodiment, there is no particular limitation as long as the surface of the second film 13 on the first adhesive layer 12 side is not subjected to a peeling treatment. For example, the second film 13 may be made of a resin sheet mainly composed of a resin material, or may be made of a paper material. As preferable examples of the material for the resin sheet and the paper constituting the second film 13, the above-mentioned material as the material of the first film 11 can be cited.
As described above, in the pressure-sensitive adhesive sheet roll 1 of the present embodiment, the thickness of the first film 11 is preferably equal to or less than the thickness of the second film 13. From the viewpoint of easily satisfying such a relationship, the thickness of the second film 13 is preferably 50 μm or more, particularly preferably 75 μm or more, and further preferably 100 μm or more. The thickness of the second film 13 is preferably 300 μm or less, particularly preferably 200 μm or less, and further preferably 150 μm or less.
The Young's modulus at 23 ℃ of the second film 13 is preferably 0.01GPa or more, more preferably 0.1GPa or more, particularly preferably 1GPa or more, and even more preferably 3GPa or more. The Young's modulus is preferably 20GPa or less, particularly preferably 10GPa or less, and further preferably 5GPa or less. By setting the young's modulus of the second film 13 at 23 ℃ to 0.01GPa or more, the form is easily maintained against the winding pressure from the first film 11 during winding, and the occurrence of wrinkles in the adhesive sheet 10 can be effectively suppressed. Further, when the young's modulus at 23 ℃ of the second film 13 is 20GPa or less, the rigidity does not become too high, and the film is easily wound.
(4) A second adhesive layer
As described above, the adhesive sheet 10 of the present embodiment preferably includes the second adhesive layer 14 laminated on the side of the second film 13 opposite to the first adhesive layer 12, and the third film 15 laminated on the side of the second adhesive layer 14 opposite to the second film 13. At this time, the laminate of the second adhesive layer 14 and the third film 15 can function as a protective film for protecting the second film 13. In general, when the adhesive sheet further includes a laminate of a second adhesive layer and a third film, the third film is added in addition to the second film as a member capable of serving as a starting point of the wrinkle. Therefore, wrinkles are particularly likely to occur in the case of the laminate having the second adhesive layer and the third film, as compared with the case of the laminate having no second adhesive layer and no third film. However, according to the adhesive sheet roll 1 of the present embodiment, even when the laminate is provided, the occurrence of wrinkles in the adhesive sheet 10 can be favorably suppressed.
The adhesive constituting the second adhesive layer 14 is not particularly limited, and may be appropriately selected according to the application. In particular, when a laminate of the second adhesive layer 14 and the third film 15 is used as the protective film, the adhesive constituting the second adhesive layer 14 is preferably an adhesive which can easily achieve an adhesive force described below and a storage modulus described below.
The adhesive constituting the second adhesive layer 14 may be any of an acrylic adhesive, a silicone adhesive, a rubber adhesive, a urethane adhesive, a polyester adhesive, a polyvinyl ether adhesive, and the like. The adhesive may be any of emulsion type, solvent type, and non-solvent type, and may be any of crosslinking type and non-crosslinking type. Further, the adhesive may be an active energy ray-curable adhesive or an inactive energy ray-curable adhesive. Among them, an acrylic adhesive curable with an actinic energy ray is preferably used as the adhesive constituting the second adhesive layer 14 in view of easily satisfying the adhesive force described below and the storage modulus described below.
When the adhesive constituting the second adhesive layer 14 of the present embodiment is an acrylic adhesive curable by actinic energy rays, such a second adhesive layer 14 can be formed, for example, from an adhesive obtained by crosslinking (thermally crosslinking) a second adhesive composition containing a (meth) acrylate copolymer (a) and a crosslinking agent (B) (hereinafter sometimes referred to as "second adhesive composition P2").
As the (meth) acrylate copolymer (a) contained in the second adhesive composition P2, for example, the same components as those of the (meth) acrylate copolymer (a) contained in the first adhesive composition P1 can be used. In particular, the (meth) acrylate copolymer (a) contained in the second adhesive composition P2 preferably contains, as monomer units constituting the polymer, a reactive group-containing monomer having a reactive group that reacts with the crosslinking agent (B) in the molecule and an alkyl (meth) acrylate having an alkyl group with 1 to 20 carbon atoms. In this case, the obtained second adhesive layer 14 has a desired cohesive force and can easily exhibit a desired adhesive force.
Preferred examples of the reactive group-containing monomer and the alkyl (meth) acrylate having an alkyl group of 1 to 20 carbon atoms in the second adhesive composition P2 include the same components as those of the monomer of the first adhesive composition P1, respectively, and particularly, the (meth) acrylate copolymer (a) contained in the second adhesive composition P2 preferably uses 4-hydroxybutyl (meth) acrylate as the reactive group-containing monomer, and preferably uses n-butyl (meth) acrylate as the alkyl (meth) acrylate having an alkyl group of 1 to 20 carbon atoms.
The (meth) acrylate copolymer (a) of the second adhesive composition P2 preferably contains 0.1% by mass or more, particularly preferably 0.5% by mass or more, and further preferably 1.0% by mass or more of a hydroxyl group-containing monomer as a monomer unit constituting the polymer. The (meth) acrylate copolymer (a) preferably contains 30% by mass or less, particularly preferably 20% by mass or less, and further preferably 10% by mass or less of a hydroxyl group-containing monomer as a monomer unit constituting the polymer.
Further, the (meth) acrylate copolymer (a) of the second adhesive composition P2 preferably contains 60 mass% or more, particularly preferably 70 mass% or more, and further preferably 80 mass% or more of an alkyl (meth) acrylate having 1 to 20 carbon atoms and an alkyl group as a monomer unit constituting the polymer. The (meth) acrylate copolymer (a) preferably contains 99.9% by mass or less, particularly preferably 99.5% by mass or less, and further preferably 99.0% by mass or less of alkyl (meth) acrylate having 1 to 20 carbon atoms and containing alkyl groups as monomer units constituting the polymer. This makes it easy to adjust the storage modulus and the adhesive force of the obtained second adhesive agent layer 14 to respective ranges described below.
The weight average molecular weight of the (meth) acrylate copolymer (a) contained in the second adhesive composition P2 is preferably 60 ten thousand or more, particularly preferably 90 ten thousand or more, and more preferably 110 ten thousand or more. The weight average molecular weight is preferably 200 ten thousand or less, particularly preferably 170 ten thousand or less, and more preferably 140 ten thousand or less. By setting the weight average molecular weight to the above range, the storage modulus of the obtained second adhesive agent layer 14 and the gel fraction of the adhesive constituting the second adhesive agent layer 14 can be easily adjusted to the ranges described below, respectively.
The crosslinking agent (B) contained in the second adhesive composition P2 can be, for example, the same component as the (meth) acrylate copolymer (a) contained in the first adhesive composition P1. Among these, as the crosslinking agent (B) contained in the second adhesive composition P2, an isocyanate-based crosslinking agent having excellent reactivity with a hydroxyl group is preferably used, particularly an aromatic polyisocyanate modified with trimethylolpropane is preferably used, and further, a tolylene diisocyanate modified with trimethylolpropane is preferably used.
The content of the crosslinking agent (B) in the second adhesive composition P2 is preferably 0.5 parts by mass or more, particularly preferably 1.0 parts by mass or more, and more preferably 2.0 parts by mass or more, relative to 100 parts by mass of the (meth) acrylate copolymer (a). The content is preferably 10 parts by mass or less, particularly preferably 7 parts by mass or less, and more preferably 5 parts by mass or less, relative to 100 parts by mass of the (meth) acrylate copolymer (a). By setting the content of the crosslinking agent (B) to the above range, the storage modulus of the obtained second adhesive agent layer 14 and the gel fraction of the adhesive constituting the second adhesive agent layer 14 can be easily adjusted to the ranges described below, respectively.
Further, as in the first adhesive composition P1, various additives commonly used in acrylic adhesives may be added to the second adhesive composition P2 as needed. As a preferable example of the additive, the same additive as that which can be added in the first adhesive composition P1 is used.
The second adhesive composition P2 can be prepared by: the (meth) acrylate copolymer (a) is prepared, and the resulting (meth) acrylate copolymer (a), the crosslinking agent (B), and the additive are mixed as needed. The preparation of the above-mentioned (meth) acrylate copolymer (a) can be performed in the same manner as the (meth) acrylate copolymer (a) contained in the first adhesive composition P1.
The thickness of the second adhesive layer 14 of the present embodiment can be appropriately set according to the use of the adhesive sheet 10. For example, the thickness is preferably 3 μm or more, particularly preferably 5 μm or more, and further preferably 7 μm or more. The thickness is preferably 40 μm or less, particularly preferably 30 μm or less, and more preferably 20 μm or less. By setting the thickness of the second adhesive layer 14 to the above range, a desired adhesive force can be easily achieved.
The storage modulus at 23 ℃ of the second adhesive layer 14 of the present embodiment is preferably 0.01MPa or more, particularly preferably 0.04MPa or more, and more preferably 0.09MPa or more. The storage modulus is preferably 3MPa or less, particularly preferably 1MPa or less, and more preferably 0.5MPa or less. By setting the storage modulus at 23 ℃ of the second adhesive layer 14 to the above range, the second adhesive layer 14 can easily suppress deformation of the third film 15 due to the winding pressure of the first film 11 and the second film 13, and can easily achieve a desired adhesive force. The method for testing the storage modulus is shown in the test examples described below.
The gel fraction of the adhesive constituting the second adhesive layer 14 of the present embodiment is preferably 60% or more, particularly preferably 80% or more, and more preferably 90% or more. The gel fraction is preferably 100% or less, particularly preferably 99% or less, and more preferably 95% or less. When the gel fraction of the adhesive constituting the second adhesive layer 14 is in the above range, the adhesive has a good cohesive force. This provides an appropriate adhesive force, and easily suppresses the generation of wrinkles in the third film 15 during winding. The method for testing the storage modulus is shown in the test examples described below.
(5) Third film
The material of the third film 15 is not particularly limited, and may be a resin sheet mainly composed of a resin material or a paper material, as in the first film 11 or the second film 13. As preferable examples of the material of the resin sheet and the paper used for the third film 15, the above-mentioned material as the material of the first film 11 can be cited.
As described above, the third film 15 can function as a protective film for protecting the second film 13 together with the second adhesive layer 14. In this case, it is preferable that the surface of the third film 15 on the side of the second adhesive agent layer 14 is not subjected to a peeling treatment from the viewpoint of suppressing peeling at the interface between the second adhesive agent layer 14 and the third film 15.
The thickness of the third film 15 is preferably 50 μm or more, particularly preferably 75 μm or more, and further preferably 100 μm or more. By setting the thickness of the third film 15 to 50 μm or more, the third film 15 easily and effectively functions as a protective film and the generation of wrinkles is easily suppressed. The thickness of the third film 15 is preferably 300 μm or less, particularly preferably 200 μm or less, and further preferably 150 μm or less. By setting the thickness of the third film 15 to 300 μm or less, the adhesive sheet 10 can be easily wound.
The Young's modulus at 23 ℃ of the third film 15 is preferably 0.01GPa or more, more preferably 0.1GPa or more, particularly preferably 1GPa or more, and even more preferably 3GPa or more. The Young's modulus is preferably 20GPa or less, particularly preferably 10GPa or less, and further preferably 5GPa or less. By setting the young's modulus of the third film 15 at 23 ℃ to 0.01GPa or more, the occurrence of wrinkles in the adhesive sheet 10 can be effectively suppressed. Further, by setting the young's modulus at 23 ℃ of the third film 15 to 20GPa or less, the second film 13 can be suppressed from having excessive rigidity, and the adhesive sheet 10 can be easily wound.
(6) Core material
The core material 20 of the present embodiment has a columnar or cylindrical shape. The diameter of the core material 20 of the present embodiment is 180mm or more. By making the diameter of the core material 20 180mm or more, the adhesive sheet roll 1 according to the embodiment of the present application can unwind the adhesive sheet 10 having an excellent appearance as described above. From this viewpoint, the diameter of the core material 20 is preferably 220mm or more, particularly preferably 260mm or more, and further preferably 290mm or more. On the other hand, the upper limit of the diameter of the core material 20 is 800mm or less, preferably 600mm or less, and particularly preferably 400mm or less, from the viewpoint of further increasing the number of windings of the adhesive sheet 10.
Although the length of the core member 20 (the length in the rotation axis direction when the adhesive sheet 10 is wound) in the present embodiment is not particularly limited, it is preferably the same as or larger than the width of the adhesive sheet 10.
The material constituting the core member 20 is not particularly limited as long as it has sufficient strength for winding the adhesive sheet 10, and conventionally known materials can be used. Examples of the material include metal, resin, and wood. Among these materials, resins are preferable, polyolefin resins are more preferable, and polypropylene is particularly preferable.
The Young's modulus at 23 ℃ of the core material 20 is preferably 0.01GPa or more, particularly preferably 0.1GPa or more, and more preferably 0.3GPa or more. The Young's modulus is preferably 500GPa or less, more preferably 100GPa or less, particularly preferably 10GPa or less, and even more preferably 1GPa or less. By setting the young's modulus at 23 ℃ of the core material 20 to the above range, the shape of the core material 20 can be favorably maintained even when the winding pressure of the adhesive sheet 10 is applied to the core material 20. The Young's modulus at 23 ℃ of the core material 20 is a value measured according to JIS Z2241: 2011.
(7) Others
In the adhesive sheet roll 1 of the present embodiment, the number of turns of the adhesive sheet 10 may be 3 or more, and particularly 10 or more. The inventors of the present application have found that when the number of windings is 3 or more, the adhesive sheet 10 unwound from the adhesive sheet roll 1 tends to have wrinkles. However, according to the adhesive sheet roll 1 of the present embodiment, even when the number of turns is 3 or more, the generation of wrinkles can be effectively suppressed. The upper limit of the number of windings may be set as appropriate from the viewpoint of the required length and amount of the adhesive sheet 10 and the operability of the adhesive sheet roll 1, and may be, for example, 2000 turns or less, and particularly 1500 turns or less.
In the adhesive sheet roll 1 of the present embodiment, the width of the adhesive sheet 10 (the length in the direction parallel to the winding axis of the adhesive sheet roll 1) may be appropriately set according to the application, and for example, the width may be 100mm or more, particularly 500mm or more, and further 900mm or more. The width may be 3000mm or less, particularly 2000mm or less, and further 1500mm or less.
2. Physical Properties of adhesive sheet
In the adhesive sheet 10 of the present embodiment, the adhesive force of the laminate of the second film 13 and the first adhesive layer 12 to soda-lime glass can be appropriately set depending on the application of the adhesive sheet 10, and is, for example, preferably 1N/25mm or more, particularly preferably 15N/25mm or more, and further preferably 40N/25mm or more. The adhesive force is preferably 100N/25mm or less, particularly preferably 80N/25mm or less, and more preferably 60N/25mm or less. When the adhesive force is in the above range, the laminate of the second film 13 and the first adhesive layer 12 can exhibit good adhesion to an adherend. Further, even when the first adhesive layer 12 is left under high-temperature and high-humidity conditions in a state of being attached to an adherend, the generation of bubbles, floating, peeling, and the like in the vicinity of the level difference is easily suppressed satisfactorily.
When the adhesive sheet 10 of the present embodiment includes the second adhesive layer 14 and the third film 15, the adhesive strength of the laminate of the third film 15 and the second adhesive layer 14 to soda-lime glass is, for example, preferably 0.01N/25mm or more, particularly preferably 0.1N/25mm or more, and more preferably 0.5N/25mm or more. The adhesive force is preferably 20N/25mm or less, particularly preferably 10N/25mm or less, and more preferably 3N/25mm or less. When the adhesive force is in the above range, the laminate of the third film 15 and the second adhesive agent layer 14 is easily and favorably adhered to the second film 13, and when the laminate is used as a protective film, the object can be easily and favorably achieved. In particular, when the adhesive sheet 10 is wound and unwound, and when it is used (when the surface of the first adhesive layer 12 opposite to the second film 13 is attached to an adherend), the protective film is easily prevented from being accidentally peeled off. At the same time, in a stage where the protective film is not necessary, adverse effects on the second film 13 and the first adhesive agent layer 12 are suppressed, and peeling and removal are easily performed satisfactorily.
The details of the above method for testing the adhesive force are shown in the test examples described later.
In the adhesive sheet 10 of the present embodiment, the peeling force when peeling the first film 11 from the laminate of the first adhesive layer 12 and the second film 13 is preferably 2000mN/25mm or less, more preferably 1000mN/25mm or less, particularly preferably 500mN/25mm or less, and further preferably 200mN/25mm or less. When the peeling force is set to 2000mN/25mm or less, the first film 11 is easily peeled from the adhesive sheet 10. The peeling force is preferably 10mN/25mm or more, particularly preferably 50mN/25mm or more, and more preferably 100mN/25mm or more. When the peeling force is set to 10mN/25mm or more, the first film 11 is easily prevented from being accidentally peeled off.
When the adhesive sheet 10 of the present embodiment includes the second adhesive layer 14 and the third film 15, the peeling force when peeling the laminate of the third film 15 and the second adhesive layer 14 from the second film 13 is preferably 3000mN/25mm or less, particularly preferably 2000mN/25mm or less, and further preferably 1000mN/25mm or less. By setting the peeling force to 3000mN/25mm or less, the laminate of the third film 15 and the second adhesive layer 14 can be easily peeled from the adhesive sheet 10. The peeling force is preferably 10mN/25mm or more, particularly preferably 100mN/25mm or more, and more preferably 200mN/25mm or more. By setting the peeling force to 10mN/25mm or more, accidental peeling of the laminate of the third film 15 and the second adhesive agent layer 14 can be easily suppressed.
The details of the above method for testing the peeling force are shown in the test examples described later.
3. Method for manufacturing adhesive sheet roll
The method for producing the adhesive sheet roll 1 of the present embodiment is not particularly limited as long as the method includes winding the adhesive sheet 10 around the core 20 with the first film 11 side as the outer side, and conventionally known methods can be employed.
When the adhesive sheet 10 of the present embodiment has a layer structure of the first film 11/the first adhesive agent layer 12/the second film 13, as an example of a method for producing the adhesive sheet 10, first, a coating solution of the first adhesive composition P1 is applied to one surface of the first film 11 (to which a peeling treatment is performed when the peeling treatment is performed). The obtained coating film was subjected to heat treatment to thermally crosslink the first adhesive composition P1, thereby forming the first adhesive layer 12. Then, by laminating one surface of the second film 13 on the surface of the first adhesive layer 12 opposite to the first film 11, the adhesive sheet 10 having a layer of the first film 11/the first adhesive layer 12/the second film 13 can be formed. If necessary, the first adhesive layer 12 may be cured. In addition, in the above-described manufacturing method, the first membrane 11 and the second membrane 13 may be exchanged.
Further, as described above, when it is difficult to form the first adhesive agent layer 12 having a desired thickness by one-time application of the coating solution, the first adhesive agent layer 12 can be formed by the following manner. That is, a laminate having an adhesive layer formed on a process sheet is prepared, and the first film 11 prepared in the above manner and the adhesive layer side surface of the laminate of adhesive layers are bonded to each other, whereby the first adhesive layer 12 having a desired thickness can be formed. At this time, the step sheet is peeled off, and the second film 13 is bonded to the exposed surface of the first adhesive layer 12, whereby the adhesive sheet 10 is obtained. Alternatively, a laminate having an adhesive layer formed on one surface of the second film 13 is prepared, and the adhesive layer side surface of the laminate of the first film 11 and the adhesive layer prepared in the above manner are bonded to each other, whereby the first adhesive layer 12 having a desired thickness can be formed, and the adhesive sheet 10 in which the first film 11, the first adhesive layer 12, and the second film 13 are sequentially laminated can be obtained.
Examples of a method for applying the coating solution of the first adhesive composition P1 include bar coating, blade coating, roll coating, blade coating, die coating, and gravure coating.
On the other hand, the adhesive sheet 10 having the layer of the first film 11/the first adhesive layer 12/the second film 13/the second adhesive layer 14/the third film 15 can be manufactured, for example, in the following manner. First, a laminate having a layer of the first film 11/the first adhesive agent layer 12/the second film 13 was obtained by the above method. In addition, a laminate having a layer of the second adhesive layer 14/the third film 15 was obtained. Then, the adhesive film can be manufactured by bonding the surface on the second adhesive layer 14 side of the laminate having the layers of the second adhesive layer 14/the third film 15 to the surface on the second film 13 side of the laminate having the layers of the first film 11/the first adhesive layer 12/the second film 13.
The laminate having the layer of the second adhesive layer 14/the third film 15 can be produced, for example, in the following manner. First, a coating solution of the second adhesive composition P2 was applied to the release-treated surface of the release sheet, and the coating film thus obtained was subjected to a heat treatment to thermally crosslink the second adhesive composition P2, thereby forming the second adhesive layer 14. Then, by laminating one surface of the third film 15 on the surface of the second adhesive layer 14 opposite to the release sheet, a laminate having a layer structure of the second adhesive layer 14/the third film 15 can be obtained in a state where the release sheet is laminated on the surface of the second adhesive layer 14 side.
The adhesive sheet 10 produced as described above is wound around the core 20, whereby the adhesive sheet roll 1 is obtained. In this winding, the adhesive sheet 10 is wound around the core 20 such that the surface of the adhesive sheet 10 on the first film 11 side is the outer side. Further, the production of the adhesive sheet 10 and the winding of the produced adhesive sheet 10 may be performed continuously. That is, the layers constituting the adhesive sheet 10 may be laminated upstream in the flow direction, and the adhesive sheet 10 obtained by finishing the lamination may be wound downstream in the flow direction.
In the above winding, tension may be applied to the adhesive sheet 10. The tension is preferably 10N/m or more, particularly preferably 50N/m or more, and more preferably 100N/m or more. The tension is preferably 1000N/m or less, particularly preferably 800N/m or less, and further preferably 500N/m or less. By winding the adhesive sheet 10 while applying a tension in the above range, the adhesive sheet roll 1 can be easily manufactured without slack and with uniform winding.
4. Method for using adhesive sheet roll
The wound adhesive sheet 1 of the present embodiment can use the unwound adhesive sheet 10 for a desired application. For example, according to the adhesive sheet roll 1 of the present embodiment, a predetermined product can be manufactured using the adhesive sheet 10 unwound from the adhesive sheet roll 1 as a process sheet. Alternatively, according to the adhesive sheet roll 1 of the present embodiment, a predetermined product can be manufactured using the adhesive sheet 10 unwound from the adhesive sheet roll 1 as a material.
Examples of products manufactured using the adhesive sheet 10 of the present embodiment as a material include display devices and semiconductor devices.
According to the adhesive sheet roll 1 of the present embodiment, since the adhesive sheet 10 in which generation of wrinkles is suppressed can be provided, a product having an excellent appearance can be manufactured by using such an adhesive sheet 10. In addition, depending on the position of the adhesive sheet 10, the presence or absence of wrinkles may affect not only the appearance of the product but also the performance of the product, and in such a case, by using the adhesive sheet roll 1 of the present embodiment, a product having excellent performance can be manufactured. From such a viewpoint, the adhesive sheet 10 of the present embodiment is suitably used for manufacturing a display device. Particularly, when a display device includes a mini-LED or a micro-LED in the inside thereof, the display device having the mini-LED or the micro-LED with excellent performance can be manufactured by using the adhesive sheet 10 of the present embodiment as an adhesive sheet directly or indirectly covering the surface of the mini-LED or the micro-LED.
A specific method of using the pressure-sensitive adhesive sheet roll 1 of the present embodiment is not particularly limited, and for example, the pressure-sensitive adhesive sheet 10 is unwound from the pressure-sensitive adhesive sheet roll 1, the first film 11 is peeled from the pressure-sensitive adhesive sheet 10, and the exposed pressure-sensitive adhesive surface of the first pressure-sensitive adhesive layer 12 is adhered to a desired adherend. When the adhesive sheet 10 includes the third film 15 and the second adhesive layer 14, the laminate of the third film 15 and the second adhesive layer 14 is peeled from the second film 13 at a desired timing. When a laminate of the third film 15 and the second adhesive layer 14 is provided as a protective film for protecting the second film 13, the laminate is preferably peeled off at a stage where protection is no longer necessary.
As described above, when the first adhesive layer 12 is composed of an active energy ray-curable acrylic adhesive, the first adhesive layer 12 can be cured by irradiating the first adhesive layer 12 with an active energy ray at a desired timing after the adhesive sheet 10 is attached to an adherend. In this case, even if there is a step or unevenness on the surface of the adherend, the first adhesive layer 12 can sufficiently follow the step or the unevenness to achieve a desired cohesive force. Thus, even when the adhesive sheet 10 is left under high-temperature and high-humidity conditions with the first adhesive layer 12 attached to an adherend, the occurrence of bubbles, floating, peeling, and the like near the level difference can be favorably suppressed.
The active energy ray irradiated on the first adhesive agent layer 12 is an active energy ray having an energy quantum in an electromagnetic wave or a charged particle beam, and specifically, an ultraviolet ray, an electron beam, or the like can be mentioned. Among the active energy rays, ultraviolet rays which are easy to handle are particularly preferable.
The irradiation of the ultraviolet ray may be performed by a high-pressure mercury lamp, fusion H lamp (fusion H lamp), xenon lamp, or the like, and the illuminance is preferably 50mW/cm with respect to the irradiation amount of the ultraviolet ray2Above 1000mW/cm2The following. The amount of ultraviolet light is preferably 50mJ/cm2Above, more preferably 80mJ/cm2Above, 200mJ/cm is particularly preferable2The above. Further, the light amount of the ultraviolet ray is preferably 10000mJ/cm2More preferably 5000mJ/cm or less2Hereinafter, the concentration is particularly preferably 2000mJ/cm2The following. On the other hand, the irradiation with the electron beam may be performed by an electron beam accelerator or the like, and the irradiation amount with the electron beam is preferably 10krad or more and 1000krad or less.
As described above, when the adhesive layer 12 made of the active energy ray-curable acrylic adhesive is attached to the first display constituent member having the step and then the active energy ray is irradiated to cure the adhesive layer 12, the adhesive layer 12 is in a state of favorably following the step, and the cohesive force of the adhesive layer 12 is improved. Thus, even when the adhesive layer 12 is left under high-temperature and high-humidity conditions in a state of being attached to an adherend, the occurrence of bubbles, floating, peeling, and the like in the vicinity of the level difference can be favorably suppressed.
As a preferred method of using the adhesive sheet roll 1 of the present embodiment, a case will be described below in which the adhesive sheet roll 1 is used in a method of manufacturing a display device provided with a mini-LED.
The above-described manufacturing method includes, for example, a sticking step of peeling the first film 11 from the adhesive sheet 10 after unwinding the adhesive sheet 10 from the adhesive sheet roll 1, and sticking the exposed surface of the exposed first adhesive layer 12 to a backlight provided with a plurality of mini-LEDs. The mini-LED may be provided on the backlight in a state of being embedded in a predetermined resin.
In addition, the manufacturing method preferably includes a cutting step of cutting the adhesive sheet 10 into a predetermined shape (for example, a shape corresponding to the backlight) before the attaching step.
When the first adhesive layer 12 is formed of an active energy ray-curable adhesive, the above-described manufacturing method preferably further includes a curing step of irradiating the first adhesive layer 12 with an active energy ray to cure the first adhesive layer 12 after the sticking step.
When the adhesive sheet 10 includes the laminate of the second adhesive layer 14 and the third film 15, it is also preferable to include a peeling step of peeling the laminate of the second adhesive layer 14 and the third film 15 from the second film 13 after the sticking step or the curing step.
According to the manufacturing method, a display device having a mini-LED with excellent performance can be manufactured.
The embodiments described above are described for easy understanding of the present invention, and are not described for limiting the present invention. Therefore, each element disclosed in the above embodiments also covers all design changes and equivalents that fall within the scope of the present invention.
Examples
The present invention will be described in more detail with reference to examples and the like, but the scope of the present invention is not limited to these examples and the like.
[ example 1]
1. Formation of the first laminate
A (meth) acrylate copolymer (a1) was prepared by copolymerizing 65 parts by mass of 2-ethylhexyl acrylate, 10 parts by mass of 4-acryloylmorpholine (N-acryloylmorpholine), 10 parts by mass of isobornyl acrylate, and 15 parts by mass of 2-hydroxyethyl acrylate by a solution polymerization method. The molecular weight of the (meth) acrylate copolymer (a1) was measured by the method described below, and as a result, the weight average molecular weight (Mw) was 60 ten thousand.
Here, the weight average molecular weight (Mw) is a weight average molecular weight in terms of polystyrene measured by Gel Permeation Chromatography (GPC) under the following conditions (GPC measurement).
< measurement conditions >
GPC measurement apparatus: HLC-8320, manufactured by TOSOH CORPORATION
GPC column (passage in the following order): TOSOH CORPORATION, Inc
TSK gel superH-H
TSK gel superHM-H
TSK gel superH2000
Determination of the solvent: tetrahydrofuran (THF)
Measurement temperature: 40 deg.C
100 parts by mass (in terms of solid content, the same shall apply hereinafter) of the (meth) acrylate copolymer (a1) obtained as described above, 0.15 part by mass of trimethylolpropane-modified toluene diisocyanate as the crosslinking agent (B), 5.0 part by mass of epsilon-caprolactone-modified tris- (2-acryloyloxyethyl) isocyanurate as the active energy ray-curable component (C), 0.5 part by mass of 2,4, 6-trimethylbenzoyl-diphenyl-phosphine oxide as the photopolymerization initiator (D), and 0.5 part by mass of 3-glycidyloxypropyltrimethoxysilane as the silane coupling agent were mixed and sufficiently stirred, and diluted with methyl ethyl ketone, thereby obtaining a coating solution of the first adhesive composition.
The coating solution of the first adhesive composition obtained in the above manner was applied to a release-treated surface of a release sheet (thickness: 75 μm, Young's modulus: 4.6GPa) obtained by subjecting one surface of a long polyethylene terephthalate film as a first film to a release treatment using a silicone-based release agent, using a blade coater. Then, the obtained coating film was dried by heating at 110 ℃ for 3 minutes, and a plurality of dried coating films were further stacked by transfer printing, thereby forming a first adhesive layer having a thickness of 250 μm.
Then, one surface of a long polyethylene terephthalate film (thickness: 100 μm, Young's modulus: 4.6GPa) as a second film was bonded to the surface of the formed first adhesive layer opposite to the first film. In this way, a first laminate having the composition of the first film/the first adhesive layer/the second film was obtained.
2. Formation of the second laminate
A (meth) acrylate copolymer (a2) was prepared by copolymerizing 99 parts by mass of n-butyl acrylate and 1 part by mass of 4-hydroxybutyl acrylate by a solution polymerization method. The molecular weight of the (meth) acrylate copolymer (a2) was measured by the above-described method, and as a result, the weight average molecular weight (Mw) was 130 ten thousand.
A coating solution of the second adhesive composition was obtained by mixing 100 parts by mass (solid content equivalent, the same applies hereinafter) of the (meth) acrylate copolymer (a2) obtained in the above-described manner and 2.0 parts by mass of trimethylolpropane-modified toluene diisocyanate as the crosslinking agent (B), sufficiently stirring, and diluting with methyl ethyl ketone.
The coating solution of the second adhesive composition obtained in the above manner was coated on one side of a long polyethylene terephthalate film (thickness: 100 μm, Young's modulus: 4.6GPa) as a third film using a blade coater. Then, the obtained coating film was subjected to a heat treatment at 110 ℃ for 1 minute, thereby drying it. Further, a release-treated surface of a release sheet (product name "SP-PET 752150" manufactured by linetec Corporation) obtained by subjecting one surface of a long polyethylene terephthalate film to a release treatment using a silicone-based release agent was bonded to a surface of the coating film opposite to the third film, and then cured at room temperature for 7 days, thereby obtaining a second laminate composed of the third film/second adhesive layer (thickness: 5 μm)/release sheet.
3. Production of adhesive sheet
The release sheet is peeled off from the second laminate obtained in the above step 2, and the exposed surface of the second adhesive layer thus exposed is bonded to the surface on the second film side of the first laminate obtained in the above step 1. Thus, a long-sized adhesive sheet (width: 1080mm) having a composition of the first film/the first adhesive layer/the second film/the second adhesive layer/the third film was obtained.
4. Production of adhesive sheet roll
The adhesive sheet obtained in the above step 3 was wound around a cylindrical core material (made of polypropylene, Young's modulus: 0.7GPa) having a diameter (outer diameter) of 304.8 mm. At this time, the adhesive sheet was wound so that the third film side was inside, and at the same time, the adhesive sheet was wound while applying a tension of 200N/m in the longitudinal direction thereof. The length of the wound adhesive sheet was set to 300 m. Thus, a wound adhesive sheet was obtained.
[ examples 2 to 8]
A wound adhesive sheet was produced in the same manner as in example 1, except that the thicknesses of the first film, the first adhesive agent layer, the second film, the second adhesive agent layer, and the third film, and the diameter of the core material were changed as shown in table 1.
[ example 9]
A (meth) acrylate copolymer (a3) was prepared by copolymerizing 55 parts by mass of 2-ethylhexyl acrylate, 10 parts by mass of 4-acryloylmorpholine (N-acryloylmorpholine), 10 parts by mass of isobornyl acrylate, and 25 parts by mass of 2-hydroxyethyl acrylate by a solution polymerization method. The molecular weight of the (meth) acrylate copolymer (a3) was measured by the above-described method, and as a result, the weight average molecular weight (Mw) was 60 ten thousand.
A wound body of an adhesive sheet was produced in the same manner as in example 1, except that a coating solution of the first adhesive composition was prepared using the obtained (meth) acrylate copolymer (a3), and the first adhesive layer was further formed using the coating solution.
[ example 10]
A wound adhesive sheet was produced in the same manner as in example 1, except that the thicknesses of the second film and the third film were changed as shown in table 1.
[ example 11]
A (meth) acrylate copolymer (a4) was prepared by copolymerizing 55 parts by mass of 2-ethylhexyl acrylate, 10 parts by mass of 4-acryloylmorpholine (N-acryloylmorpholine), 10 parts by mass of isobornyl acrylate, and 25 parts by mass of 2-hydroxyethyl acrylate by a solution polymerization method. The molecular weight of the (meth) acrylate copolymer (a4) was measured by the above-described method, and as a result, the weight average molecular weight (Mw) was 60 ten thousand.
100 parts by mass of the obtained (meth) acrylate copolymer (A4), 2.0 parts by mass of trimethylolpropane-modified tolylene diisocyanate as the crosslinking agent (B), and 0.5 parts by mass of 3-glycidyloxypropyltrimethoxysilane as the silane coupling agent were mixed, sufficiently stirred, and diluted with methyl ethyl ketone to obtain a coating solution of the first adhesive composition.
An adhesive sheet roll was produced in the same manner as in example 1, except that the first adhesive layer was formed using the obtained coating solution of the first adhesive composition.
Comparative example 1
An adhesive sheet roll was produced in the same manner as in example 1, except that the diameter of the core material was changed as shown in table 1.
[ test example 1] (measurement of storage modulus of adhesive agent layer)
The first adhesive layers prepared in the examples and comparative examples were laminated to prepare a laminate having a thickness of 3 mm. From the laminate of the obtained first adhesive layer, a cylindrical body (height 3mm) having a diameter of 8mm was punched out, and this was used as a sample.
For the above sample, storage modulus (G') (MPa) was measured by a torsional shear method (ね, manufactured by sliding on りせ once) according to JIS K7244-6:1999 using a viscoelasticity measuring instrument (product name "DYNAMIC ANALYZER" manufactured by REMOTRIC) under the following conditions. The results are shown in table 1 as the storage modulus of the first adhesive agent layer before ultraviolet irradiation (before UV irradiation).
Measuring frequency: 1Hz
Measuring temperature: 23 deg.C
Further, with respect to the sample obtained in the same manner as described above, the first adhesive agent layer constituting the sample was cured by irradiating ultraviolet rays under the following conditions. For this cured sample, the storage modulus (G') (MPa) was also measured in the same manner as described above. The results are shown in table 1 as the storage modulus of the first adhesive agent layer after ultraviolet irradiation (after UV irradiation).
< ultraviolet irradiation conditions >
Using high-pressure mercury lamps
Illuminance of 200mW/cm2Light quantity 1000mJ/cm2
UV illuminance/photometer Using "UVPF-A1" manufactured by Eye graphics Co., Ltd "
Further, the second adhesive agent layers prepared in examples and comparative examples were also measured for storage modulus (G') (MPa) before irradiation with ultraviolet rays in the same manner as described above. The results are also shown in Table 1.
[ test example 2] (measurement of gel fraction)
The first laminate (the first film/the first adhesive layer/the second film) obtained in examples and comparative examples was cut into a size of 80mm × 80mm, the first adhesive layer was wrapped in a polyester mesh (mesh size 200), the mass thereof was weighed using a precision balance, and the mass of the mesh alone was subtracted, thereby calculating the mass of the adhesive itself constituting the first adhesive layer. The mass at this time was designated as M1.
Then, the above-mentioned adhesive wrapped with a polyester mesh was immersed in ethyl acetate at room temperature (23 ℃) for 24 hours. The adhesive was then taken out, air-dried at a temperature of 23 ℃ and a relative humidity of 50% for 24 hours, and further dried in an oven at 80 ℃ for 12 hours. After drying, the mass was weighed using a precision balance, and the mass of the web alone was subtracted, thereby calculating the mass of the adhesive itself. The mass at this time was designated as M2.
The values of masses M1 and M2 obtained in the above manner were substituted into a calculation formula of (M2/M1) × 100 to calculate the gel fraction (%). The results are shown in table 1 as the gel fraction (%) of the first adhesive agent layer before ultraviolet irradiation (before UV irradiation).
Further, the gel fraction (%) of the first adhesive agent layer cured by irradiation with ultraviolet rays under the ultraviolet irradiation conditions described in test example 1 was also calculated in the same manner as described above. The results are shown in table 1 as the gel fraction (%) of the first adhesive agent layer after irradiation with ultraviolet rays (after UV irradiation).
Further, the gel fraction (%) before irradiation with ultraviolet rays was calculated for the second adhesive agent layers prepared in examples and comparative examples in the same manner as described above. The results are also shown in Table 1.
[ test example 3] (measurement of adhesive force)
The first laminate (the first film/the first adhesive layer/the second film) obtained in examples and comparative examples was cut into a width of 25mm and a length of 100 mm. Then, the first film was peeled off from the first laminate, and the exposed surface of the exposed second adhesive agent layer was attached to soda-lime Glass (manufactured by Nippon Sheet Glass co., ltd.) under an atmosphere of 23 ℃ and 50% RH, and pressurized at 0.5MPa and 50 ℃ for 20 minutes using an autoclave (manufactured by kurihia sesisakusho co., ltd.).
Then, the first adhesive agent layers of examples 1 to 10 and comparative example 1 were cured by irradiating ultraviolet rays through a PET film under the conditions described in test example 1.
Then, after being left at 23 ℃ and 50% RH for 24 hours, the adhesion (N/25mm) was measured under conditions of a peeling speed of 300 mm/min and a peeling angle of 180 degrees using a tensile tester (ORIENTEC co., ltd., product name "TENSILON"). The conditions not described herein were measured according to JIS Z0237: 2009. The results are shown in Table 1.
In addition, the second laminate (the third film/the second adhesive layer/the release sheet) obtained in the examples and comparative examples was also measured for the adhesive force (N/25mm) in the same manner as described above. However, the surface of the second adhesive layer bonded to the soda-lime glass is set as an exposed surface of the second adhesive layer exposed by peeling the release sheet from the second laminate, and the second adhesive layer is not irradiated with ultraviolet rays. The results are also shown in Table 1.
[ test example 4] (measurement of peeling force)
The adhesive sheets produced in examples and comparative examples were cut into a length of 100mm and a width of 25 mm. Then, the surface of the adhesive sheet on the first film side was fixed to a stainless steel plate, thereby obtaining a sample for measuring a peeling force.
The above-described sample for measuring the peeling force was measured for the force at the time of peeling the laminate of the third film and the second adhesive layer from the second film at a peeling angle of 180 ° and a peeling speed of 0.3 m/min using a tensile tester (ORIENTEC co., ltd., product name "tens on UTM-4-100") under a standard environment (23 ℃, 50% RH) based on JIS Z0237:2009, and the force was taken as the peeling force (mN/25mm) at the interface between the second adhesive layer and the second film. The results are shown in Table 1.
Then, in the same manner as described above, the laminate of the second film and the first adhesive layer was peeled from the first film, and the force measured at this time was taken as the peeling force (mN/25mm) of the interface between the first adhesive layer and the first film. The results are also shown in Table 1.
[ test example 5] (evaluation of step tracking Property)
An ultraviolet curable ink (TEIKOKU PRINTING INKS mfg. co., ltd., product name "POS-911 SUMI") was screen-printed in a frame shape (outer shape: 90mm long × 50mm wide, 5mm wide) on a surface of a Glass plate (NSG PRECISION, product name "CORNING Glass EAGLE XG", 90mm long × 50mm wide × 0.5mm thick) so that the coating thickness was 10 μm. Then, ultraviolet rays (80W/cm) were irradiated22 metal halogen lamps with the lamp height of 15cm and the belt speed of 10-15 m/min,the printed ultraviolet curable ink was cured to prepare a stepped glass plate having a step (height of step: 10 μm) by printing. Further, a stepped glass plate was produced in which the height of the step due to printing was changed to 5 μm.
On the other hand, the coating solutions of the first adhesive compositions prepared in examples and comparative examples were applied to the release-treated surface of the first release sheet obtained by subjecting one surface of a polyethylene terephthalate film to a release treatment using a silicone-based release agent, using a blade coater. The obtained coating film was dried by heat treatment at 110 ℃ for 3 minutes, thereby forming a first adhesive layer. The thickness of the first adhesive agent layer formed at this time was made the same as the thickness of the first adhesive agent layer in the adhesive sheet roll of the example and comparative example, respectively. Then, the release-treated surface of the second release sheet obtained by subjecting one surface of the polyethylene terephthalate film to a release treatment using a silicone-based release agent was bonded to the surface of the first adhesive layer opposite to the first release sheet, thereby obtaining a sample for evaluation.
The first film was peeled off from the obtained evaluation sample to expose the first adhesive layer, and the two types of stepped glass plates obtained in the above manner were laminated using a laminator (manufactured by fujiapla inc., product name "LPD 3214") so that the first adhesive layer covered the entire frame-shaped printing surface. Further, the second film was peeled off from each of the first adhesive layers, and one surface of the glass plate (without a printing step) was bonded to the exposed surface of the exposed first adhesive layer.
The laminate having a structure of a glass plate with a step (height of step: 10 μm or 5 μm)/a first adhesive agent layer/a glass plate (no printing step) obtained in the above manner was subjected to a heat press treatment for 30 minutes at 50 ℃ and 0.5MPa, and left to stand at normal pressure, 23 ℃ and 50% RH for 24 hours. Then, the first adhesive layer was irradiated with ultraviolet rays through the glass plate (without a print step) under the same conditions as in test example 3, and the first adhesive layer was cured.
Then, the resultant was stored at 85 ℃ and 85% RH for 72 hours (durability test). Then, the presence or absence of air bubbles, floating, and peeling at the interface between the printed step and the cured first adhesive layer was visually confirmed, and the step followability was evaluated according to the following criteria. The results are shown in Table 1.
Very good: when the height of the printing step was 10 μm or 5 μm, no bubble, lifting and peeling were generated.
Good: when the height of the printing step is 10 μm, at least one of air bubbles, lifting and peeling is generated, but when the height of the printing step is 5 μm, air bubbles, lifting and peeling are not generated.
X: when the height of the printing step is 10 μm and 5 μm, at least one of air bubbles, floating, and peeling is generated.
[ test example 6] (evaluation of appearance of adhesive sheet)
All adhesive sheets were unwound from the adhesive sheet rolls obtained in examples and comparative examples 7 days after the production, and appearance abnormalities such as creases and deformed wrinkles were visually observed over the entire length (300m), and the appearance of the adhesive sheets was evaluated according to the following criteria. The results are shown in Table 1. In the following reference, "5 m" means a position 5m away from the end portion on the core material side of the adhesive sheet in the unwinding direction of the wound adhesive sheet, and other similar expressions are also used. The appearance abnormality does not include a mark caused by a tape for fixing the adhesive sheet to the core member.
Very good: at least between 5m and 300m, no appearance abnormality was generated.
Good: although the appearance abnormality is generated between 0m and 10m, the appearance abnormality is not generated between 10m and 300 m.
And (delta): although the appearance abnormality is generated between 0m and 30m, the appearance abnormality is not generated between 30m and 300 m.
X: appearance abnormality was generated between 30m and 300 m.
As can be seen from table 1, the adhesive sheet roll obtained in the examples can unwind an adhesive sheet having an excellent appearance.
Industrial applicability
The pressure-sensitive adhesive sheet roll of the present invention is suitably used, for example, for manufacturing a display device, and particularly suitably used for manufacturing a backlight including a mini-LED or a micro-LED as a light source in the display device.
Claims (6)
1. An adhesive sheet roll comprising a long adhesive sheet provided with a first film, a first adhesive layer laminated on one surface of the first film, and a second film laminated on the first adhesive layer on the side opposite to the first film, the long adhesive sheet being wound around a cylindrical or cylindrical core member with the surface on the first film side as the outer side, the adhesive sheet roll being characterized in that,
the diameter of the core material is more than 180mm and less than 800mm,
the surface of the second film on the first adhesive layer side is not subjected to a peeling treatment.
2. The adhesive sheet roll according to claim 1, wherein the thickness of the first film is equal to or less than the thickness of the second film.
3. The pressure-sensitive adhesive sheet roll according to claim 1, wherein a peeling force when peeling the first film from a laminate of the first adhesive layer and the second film is 10mN/25mm or more and 2000mN/25mm or less.
4. The wound adhesive sheet according to claim 1, wherein the adhesive sheet comprises: a second adhesive layer laminated on one side of the second film opposite to the first adhesive layer; a third film laminated on the second adhesive layer on a side opposite to the second film.
5. The wound adhesive sheet according to claim 4, wherein the adhesive force of the laminate of the third film and the second adhesive layer to soda-lime glass is 0.01N/25mm or more and 20N/25mm or less.
6. The wound adhesive sheet according to claim 1, wherein the first adhesive layer has a storage modulus at 23 ℃ of 0.001MPa or more and 1.00MPa or less.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2019150589A JP7477948B2 (en) | 2019-08-20 | 2019-08-20 | Adhesive sheet roll |
| JP2019-150589 | 2019-08-20 |
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| Publication Number | Publication Date |
|---|---|
| CN112409935A true CN112409935A (en) | 2021-02-26 |
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202010761033.3A Pending CN112409935A (en) | 2019-08-20 | 2020-07-31 | Adhesive sheet roll |
Country Status (4)
| Country | Link |
|---|---|
| JP (1) | JP7477948B2 (en) |
| KR (1) | KR20210022487A (en) |
| CN (1) | CN112409935A (en) |
| TW (1) | TW202111045A (en) |
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| JPH11109131A (en) * | 1997-10-02 | 1999-04-23 | Nippon Synthetic Chem Ind Co Ltd:The | Method for storing layered product |
| CN106916540A (en) * | 2015-10-16 | 2017-07-04 | 琳得科株式会社 | Adhesive sheet and display body |
| JP2018169372A (en) * | 2017-03-30 | 2018-11-01 | リンテック株式会社 | Calculation system, calculation method, winding method, and wound roll body |
| JP2019127527A (en) * | 2018-01-24 | 2019-08-01 | 日東電工株式会社 | Laminate sheet and roll |
Family Cites Families (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| ES247427Y (en) | 1977-05-31 | 1981-06-16 | A PERFECTED CONTAINER WITH TWO COMPARTMENTS INTENDED TO CONTAIN PRODUCTS SEPARATED FROM EACH OTHER. | |
| JP2010185037A (en) | 2009-02-13 | 2010-08-26 | Mitsubishi Plastics Inc | Adhesive sheet and method for producing the same |
| JP6055171B2 (en) | 2011-07-29 | 2016-12-27 | 住友化学株式会社 | Polarizing plate roll and manufacturing method thereof |
| JP2018161783A (en) | 2017-03-24 | 2018-10-18 | 日東電工株式会社 | Resin shee with surface layer material |
| JP7067073B2 (en) | 2018-01-16 | 2022-05-16 | 昭和電工マテリアルズ株式会社 | Adhesive sheet roll and its manufacturing method, and semiconductor device manufacturing method |
| JP7025231B2 (en) | 2018-02-01 | 2022-02-24 | 日東電工株式会社 | Surface protective film |
| JP7138448B2 (en) | 2018-02-22 | 2022-09-16 | リンテック株式会社 | Adhesive sheet roll |
-
2019
- 2019-08-20 JP JP2019150589A patent/JP7477948B2/en active Active
-
2020
- 2020-06-08 TW TW109119163A patent/TW202111045A/en unknown
- 2020-06-30 KR KR1020200080085A patent/KR20210022487A/en active Search and Examination
- 2020-07-31 CN CN202010761033.3A patent/CN112409935A/en active Pending
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH11109131A (en) * | 1997-10-02 | 1999-04-23 | Nippon Synthetic Chem Ind Co Ltd:The | Method for storing layered product |
| CN106916540A (en) * | 2015-10-16 | 2017-07-04 | 琳得科株式会社 | Adhesive sheet and display body |
| JP2018169372A (en) * | 2017-03-30 | 2018-11-01 | リンテック株式会社 | Calculation system, calculation method, winding method, and wound roll body |
| JP2019127527A (en) * | 2018-01-24 | 2019-08-01 | 日東電工株式会社 | Laminate sheet and roll |
Also Published As
| Publication number | Publication date |
|---|---|
| TW202111045A (en) | 2021-03-16 |
| KR20210022487A (en) | 2021-03-03 |
| JP7477948B2 (en) | 2024-05-02 |
| JP2021031539A (en) | 2021-03-01 |
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